JP5640439B2 - Polypropylene resin composition and molded body - Google Patents

Description

  The present invention relates to a polypropylene resin composition and a molded body.

Polypropylene resin compositions are materials that are excellent in mechanical properties and the like, and are therefore used for interior and exterior parts of automobiles and parts of electrical products.
For example, in Patent Document 1, various additives such as an antioxidant and a neutralizing agent are added to a resin composition in which a domain made of propylene / α-olefin copolymer is dispersed in a matrix made of crystalline polypropylene. The fact that it is added is described.
Patent Document 2 describes a resin composition containing a propylene polymer nucleated with a polymeric nucleating agent containing a vinyl compound unit and talc.
Patent Document 3 describes a resin composition containing a polyolefin matrix and a nucleating agent dispersed or dissolved in the matrix.

International Publication Number WO99 / 57195 Special table 2001-522916 Special table 2009-508995

However, molded articles made of the resin compositions described in these documents have a problem that the molding shrinkage ratio is large although they are excellent in mechanical properties such as impact resistance and rigidity. In the case of producing a large molded body, there has been a problem that the dimensional change of the molded body is particularly large.
In addition, it is required to increase the crystallization rate of the resin composition, shorten the molding cycle, and further improve the productivity.
In view of the above problems, an object of the present invention is to provide a polypropylene resin composition and a molded body that maintain the mechanical characteristics of a conventional molded body, have a small molding shrinkage rate, and have a high crystallization speed.

The present invention comprises propylene polymer (A) 50 to 98% by weight, ethylene polymer (B) 1 to 40% by weight having a density of 0.85 to 0.93 (g / cm ³ ) , talc and / or Inorganic filler (C) that is a fibrous inorganic filler (C) 8-30 wt% (the total weight of the (A), (B) and (C) is 100 wt%),
Inclusive of 0.001 to 1.0 part by weight of at least one metal salt (D) represented by the following general formula (I) with respect to 100 parts by weight of the total amount of (A), (B) and (C). A polypropylene resin composition is provided.

〔式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して水素原子、炭素原子数１〜９個のアルキル基、水酸基、炭素原子数１〜９個のアルコキシ基、ハロゲン原子、フェニル基及び下記一般式（ＩＩ）、（ＩＩＩ）からなる群から選択されるいずれかの基である。ここで、これらの基のうち互いに隣接する少なくとも２つの基がアルキル基である場合、これらのアルキル基同士は結合して炭素原子数６個までの炭素環を形成してよい。この化合物のＲ^１とＲ^２はシス配置である。〕
−（Ｒ^１１Ｏ）ｎ−Ｘ・・・（ＩＩ）
〔式中、Ｒ^１１は、炭素原子数１〜９個のアルキレン基を表し、ｎは１〜９の整数を表し、Ｘは水素原子、炭素原子数１〜９個のアルキル基、ベンゾイル基、フェニル基、炭素原子数１〜９個のアルキル基及び／又はハロゲン原子によって置換されたベンゾイル基、炭素原子数１〜９個のアルキル基及び／又はハロゲン原子によって置換されたフェニル基を表す。〕
−ＮＲ^１２Ｒ^１３・・・（ＩＩＩ）
〔式中、Ｒ^１２及びＲ^１３は、それぞれ独立して水素原子、炭素原子数１〜９個のアルキル基からなる群から選択される基である。〕

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, having 1 to 9 carbon atoms. An alkyl group, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, a halogen atom, a phenyl group and any group selected from the group consisting of the following general formulas (II) and (III). Here, when at least two groups adjacent to each other among these groups are alkyl groups, these alkyl groups may be bonded to each other to form a carbocyclic ring having up to 6 carbon atoms. In this compound, R ¹ and R ² are in a cis configuration. ]
^{- (R 11 O) n-} X ··· (II)
[Wherein R ¹¹ represents an alkylene group having 1 to 9 carbon atoms, n represents an integer of 1 to 9, X represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a benzoyl group, It represents a phenyl group, a benzoyl group substituted with an alkyl group having 1 to 9 carbon atoms and / or a halogen atom, an alkyl group having 1 to 9 carbon atoms and / or a phenyl group substituted with a halogen atom. ]
-NR ¹² R ¹³ (III)
[Wherein, R ¹² and R ¹³ are each independently a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 9 carbon atoms. ]

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the polypropylene resin composition and molded object which maintain the mechanical characteristic of the conventional molded object, are small in a mold shrinkage rate, and are high crystallization speed.

[Polypropylene resin composition]
A polypropylene resin composition according to the present invention (hereinafter also simply referred to as a resin composition) comprises a propylene polymer (A), an ethylene polymer (B), an inorganic filler (C), and a metal salt (D). contains. Hereinafter, each component will be described.
[Propylene polymer (A)]
The propylene polymer (A) (hereinafter also referred to as the component (A)) 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. The copolymer may be a random copolymer or a block copolymer.
As the random copolymer, a random copolymer comprising a structural unit derived from propylene and a structural unit derived from ethylene; random copolymer consisting of a structural unit derived from propylene and a structural unit derived from an α-olefin other than propylene Random copolymer consisting of a structural unit derived from propylene, a structural unit derived from ethylene, and a structural unit derived from an α-olefin other than propylene is exemplified.
The block copolymer includes a propylene homopolymer component or a polymer component composed of propylene-derived structural units (hereinafter referred to as polymer component (I)), and a copolymer of propylene and ethylene and / or α-olefin. Examples thereof include a polymerization material composed of a coalescence component (hereinafter referred to as polymer component (II)).

The propylene polymer (A) is expressed as an isotactic pentad fraction ([mmmm] fraction measured by ¹³ C-NMR from the viewpoint of the balance between the tensile strength and impact resistance of the resin composition. Is preferably 0.97 or more, and more preferably 0.98 or more. The isotactic pentad fraction is a value determined by a measurement method described later. The closer the isotactic pentad fraction of the propylene polymer (A) is to 1, the higher the propylene polymer (A) is. It is an index showing that it is a highly crystalline polymer having a molecular structure exhibiting stereoregularity.
When the propylene polymer (A) is the random copolymer or the block copolymer, a value measured for a chain of propylene units in the copolymer is used.

  The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of the propylene copolymer (A) is the balance between the tensile strength and impact resistance of the resulting molded product, and the molding processability of the resin composition. From the viewpoint, it is preferably 0.5 to 200 g / 10 minutes, more preferably 1 to 100 g / 10 minutes, further preferably 2 to 80 g / 10 minutes, and 5 to 50 g / 10 minutes. Most preferably it is.

The propylene polymer (A) can be produced by the following method using a polymerization catalyst.
Examples of the polymerization catalyst include a Ziegler type catalyst system, a Ziegler-Natta type catalyst system, a catalyst system comprising a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane, or a cyclopentadienyl ring. Periodic table having a cyclopentadienyl ring in inorganic particles such as silica, clay minerals, catalyst systems composed of compounds and organoaluminum compounds that react with group 4 transition metal compounds and ionic complexes. Examples include a catalyst system in which a catalyst component such as a Group 4 transition metal compound, a compound that forms an ionic complex, and an organoaluminum compound is supported and modified. In addition, in the presence of the above catalyst system, ethylene or α -A prepolymerization catalyst prepared by prepolymerizing olefin may be used.
Examples of the catalyst system include JP-A-61-218606, JP-A-5-194485, JP-A-7-216071, JP-A-9-316147, JP-A-10-212319, Examples thereof include a catalyst system described in JP-A-2004-182981.

Examples of the polymerization method include bulk polymerization, solution polymerization, slurry polymerization, and gas phase polymerization. Here, bulk polymerization refers to a method in which polymerization is performed using a liquid olefin as a medium at the polymerization temperature, and solution polymerization or slurry polymerization refers to inert hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane. A method for carrying out polymerization in a solvent. Gas phase polymerization is a method in which a gaseous monomer is used as a medium, and the gaseous monomer is polymerized in the medium.
These polymerization methods may be either a batch type or a multi-stage type in which a plurality of polymerization reaction vessels are connected in series, and these polymerization methods may be arbitrarily combined. From an industrial and economical viewpoint, a continuous gas phase polymerization method or a bulk-gas phase polymerization method in which a bulk polymerization method and a gas phase polymerization method are continuously performed is preferable.
Various conditions in the polymerization step (polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) may be appropriately determined according to the target propylene polymer (A).

  In the production of the propylene polymer (A), in order to remove the residual solvent contained in the propylene polymer (A), the ultra-low molecular weight oligomer by-produced during the production, etc. ) May be dried at a temperature below the temperature at which the propylene polymer (A) melts. Examples of the drying method include the methods described in JP-A Nos. 55-75410 and 2556553.

<Random copolymer>
As described above, the random copolymer in the present invention is a random copolymer comprising a structural unit derived from propylene and a structural unit derived from ethylene; a structural unit derived from a structural unit derived from propylene and an α-olefin other than propylene. A random copolymer consisting of 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 and the like can be mentioned, and 1-butene, 1-hexene and 1-octene are preferable.

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

  The content of the structural unit 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. .

<Block copolymer>
As described above, the block copolymer in the present invention includes a propylene homopolymer component or a polymer component composed of propylene-derived structural units (hereinafter referred to as polymer component (I)), propylene, ethylene, and / or Or the polymeric material which consists of a copolymer component (henceforth polymer component (II)) with an alpha olefin.
The polymer component (I) is a polymer component composed of a propylene homopolymer component or a structural unit derived from propylene. The polymer component composed of propylene-derived constitutional units is composed of units derived from at least one comonomer selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms, and units derived from propylene. And a propylene copolymer component.

When the polymer component (I) is a polymer component composed of propylene-derived structural units, it is derived from at least one comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. The content of the unit is 0.01 to 30% 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 composed of propylene-derived constituent units include a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, and a propylene-1-octene copolymer. Examples of the polymer component include 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 a copolymer having 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 polymer 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 1 to 80% by weight. Yes, preferably 5 to 60% by weight, more preferably 20 to 60% by weight (provided that the weight of the polymer component (II) is 100% by weight).

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

  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, etc., preferably propylene-ethylene copolymer component, propylene-1-butene copolymer component, propylene-ethylene-1-butene copolymer component, more preferably propylene- It is an 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. 10 to 40% by weight is more preferable, and 10 to 30% by weight is most preferable (provided that the weight of the propylene polymer (A) is 100% by weight).

  When the polymer component (I) of the propylene copolymer composed of 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) Examples thereof include a copolymer and a (propylene)-(propylene-1-decene) copolymer.

  When the polymer component (I) of the polymer material composed of the polymer component (I) and the polymer component (II) is a propylene copolymer component composed of units derived from propylene, the polymer component (I) and the polymer Examples of the propylene copolymer comprising 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 Polymer, (propylene-1-butene)-(propylene-ethylene-1-octene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-decene) copolymer, (propylene-1-butene) )-(Propylene-1-butene) copolymer, (propylene-1-butene)-(propylene-1-hexene) copolymer, (propylene-1-butene) )-(Propylene-1-octene) copolymer, (propylene-1-butene)-(propylene-1-decene) copolymer, (propylene-1-hexene)-(propylene-1-hexene) copolymer Polymer, (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, (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 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. It is.

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 2 to 2. 10, more preferably 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 (A) is a polymer material obtained by multi-stage polymerization of the polymer component (I) and the polymer component (II), the polymer component is extracted from the polymer powder partially extracted from the previous polymerization tank. The intrinsic viscosity of (I) or 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 by polymerizing the polymer component (I) in the preceding step and obtaining the polymer component (II) in the subsequent step. Content of polymer component (I) and polymer component ( _II ), measurement of intrinsic viscosity ([η] _Total , [η] _I , [η] _II ) The calculation procedure is as follows. The intrinsic viscosity ([η] _Total ) indicates the intrinsic viscosity of the entire propylene polymer (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 × XI) / XII
[Η] _Total : Intrinsic viscosity (dl / g) of the final polymer after the subsequent polymerization step
[Η] _I : Intrinsic viscosity (dl / g) of the polymer powder extracted from the polymerization tank after the pre-stage polymerization step
XI: Weight ratio of the polymer component (I) to the entire propylene polymer (A) XII: Weight ratio of the polymer component (II) to the entire propylene polymer (A) Note that XI and XII are from the material balance during polymerization. Ask.

  The block copolymer is obtained by producing the polymer component (I) in the first step and producing the polymer component (II) in the second step. The polymerization is performed using the above-described polymerization catalyst.

[Ethylene polymer (B)]
The ethylene polymer (B) (hereinafter also referred to as the component (B)) in the present invention means an ethylene polymer having a density of 0.85 to 0.93 (g / cm ³ ), and even an ethylene homopolymer or ethylene And a copolymer of α-olefin may be used.
Specifically, a high-pressure method low-density polyethylene (g / cm ³ ) having a density of 0.91 to 0.93 (g / cm ³ ) in which ethylene of repeating units is randomly bonded with a branched structure by high-pressure radical polymerization using a radical initiator. LDPE).

As a copolymer of ethylene and α-olefin, for example, a linear low density polyethylene having a crystallinity in a range of 0.90 to 0.93 (g / cm ³ ), or a density of 0.85. Examples thereof include copolymers of ethylene and α-olefin having low crystallinity and rubber-like elastic properties in a range of ˜0.90 (g / cm ³ ).

  The α-olefin used for the production of the ethylene polymer (B) is the above-mentioned α-olefin having 4 to 10 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 4-methyl- Examples include 1-pentene, 1-octene, 1-decene, α-olefins having a cyclic structure, and preferably 1-butene, 1-hexene, and 1-octene.

  The ethylene polymer (B) is preferably a copolymer of ethylene and α-olefin. Specifically, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, ethylene- (3-methyl-1- Butene) copolymer, a copolymer of ethylene and an α-olefin having a cyclic structure, and the like.

  The content of the α-olefin contained in the ethylene polymer (B) is preferably 1 to 49% by weight, more preferably 5 to 49% by weight, still more preferably 10 to 49% by weight (ethylene The weight of the polymer (B) is 100% by weight).

The melt flow rate of the ethylene polymer (B) measured at 190 ° C. and 2.16 kg load is preferably 0.5 to 50 g / 10 min. MFR _B is more preferably 1 to 30 g / 10 minutes, and further preferably 1 to 20 g / 10 minutes.

The ethylene polymer (B) 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.
In addition, when using a high pressure process low density polyethylene (LDPE), a radical initiator can be used as a polymerization catalyst.

  As the ethylene polymer (B), a known commercial product may be used. 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.

[Inorganic filler (C)]
The inorganic filler (C) in the present invention (hereinafter also referred to as the component (C)) refers to a non-fibrous inorganic filler or a fibrous inorganic filler.
Non-fibrous inorganic fillers include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, calcium sulfate, silica sand, carbon black, titanium oxide, magnesium hydroxide, zeolite, molybdenum, diatom Examples include soil, sericite, shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, bentonite, and graphite. These may be used alone or in combination of two or more. Of these, talc is preferably used.
The non-fibrous inorganic filler may be used as it is, but in order to improve the interfacial adhesion with the propylene polymer (A) and improve the dispersibility with respect to the propylene polymer (A). 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 diameter of the non-fibrous inorganic filler is 10 μm or less, 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.
Examples of the non-fibrous inorganic filler include powder, flakes, and granules, and any form may be used.

Examples of the fibrous inorganic filler 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. Can be mentioned. 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 fibrous inorganic filler may be used without treatment, but in order to improve the interfacial adhesion with the propylene polymer (A) and improve the dispersibility with respect to the propylene polymer (A), 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 fibrous inorganic filler measured by electron microscope observation is 3 μm or more, preferably 3 μm to 20 μm, more preferably 8 μm 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 they are 0.2 micrometer-1.5 micrometers, More preferably, they are 0.3 micrometer-1.0 micrometer.

[Metal salts (D)]
In the present invention, the metal salt (D) (hereinafter also referred to as the component (D)) refers to at least one metal salt represented by the following general formula (I).

〔式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して水素原子、炭素原子数１〜９個のアルキル基、水酸基、炭素原子数１〜９個のアルコキシ基、ハロゲン原子、フェニル基及び下記一般式（ＩＩ）、（ＩＩＩ）からなる群から選択されるいずれかの基である。ここで、これらの基のうち互いに隣接する少なくとも２つの基がアルキル基である場合、これらのアルキル基同士は結合して炭素原子数６個までの炭素環を形成してよい。この化合物のＲ^１とＲ^２はシス配置である。〕
−（Ｒ^１１Ｏ）ｎ−Ｘ・・・（ＩＩ）
〔式中、Ｒ^１１は、炭素原子数１〜９個のアルキレン基を表し、ｎは１〜９の整数を表し、Ｘは水素原子、炭素原子数１〜９個のアルキル基、ベンゾイル基、フェニル基、炭素原子数１〜９個のアルキル基及び／又はハロゲン原子によって置換されたベンゾイル基、炭素原子数１〜９個のアルキル基及び／又はハロゲン原子によって置換されたフェニル基を表す。〕
−ＮＲ^１２Ｒ^１３・・・（ＩＩＩ）
〔式中、Ｒ^１２及びＲ^１３は、それぞれ独立して水素原子、炭素原子数１〜９個のアルキル基からなる群から選択される基である。〕

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, having 1 to 9 carbon atoms. An alkyl group, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, a halogen atom, a phenyl group and any group selected from the group consisting of the following general formulas (II) and (III). Here, when at least two groups adjacent to each other among these groups are alkyl groups, these alkyl groups may be bonded to each other to form a carbocyclic ring having up to 6 carbon atoms. In this compound, R ¹ and R ² are in a cis configuration. ]
^{- (R 11 O) n-} X ··· (II)
[Wherein R ¹¹ represents an alkylene group having 1 to 9 carbon atoms, n represents an integer of 1 to 9, X represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a benzoyl group, It represents a phenyl group, a benzoyl group substituted with an alkyl group having 1 to 9 carbon atoms and / or a halogen atom, an alkyl group having 1 to 9 carbon atoms and / or a phenyl group substituted with a halogen atom. ]
-NR ¹² R ¹³ (III)
[Wherein, R ¹² and R ¹³ are each independently a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 9 carbon atoms. ]

In the above compounds, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen or 1 to 3 carbon atoms. A compound that is an alkyl group is preferable, and a cis-1,2-cyclohexanedicarboxylate calcium salt represented by the following structural formula is more preferable.

The metal salt (D) may be used by mixing with a dispersant in order to improve dispersibility in the resin composition containing the propylene polymer (A), the ethylene polymer (B), and the inorganic filler (C). Good. Examples of the dispersant include fatty acids, fatty acid alkyl esters, fatty acid metal salts, hydrocarbon-substituted alcohols having 10 to 30 carbon atoms, polyhydric alcohols, and esters thereof.
The fatty acid is a fatty acid having 10 to 24 carbon atoms, and the metal salt of the fatty acid is a metal salt of an alkyl metal or an alkaline earth metal. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the alkali metal include calcium, magnesium, and zinc. Examples of the polyhydric alcohol and esters thereof include glycerin, ethylene glycol, propylene glycol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, and esters thereof. Of these, metal salts of fatty acids are preferably used.

  The form of the metal salt (D) is preferably particulate. As a particle diameter of metal salts (D), the average particle diameter calculated | required by the laser diffraction type particle size distribution measuring method is 0.01-10 micrometers, Preferably it is 0.01-5 micrometers, More preferably, 0.01- 3 μm. The laser diffraction particle size distribution measuring method is a method for measuring the particle size distribution using a laser diffraction particle size distribution measuring device (HELOS (trade name) manufactured by Sympatec).

  Examples of the method for producing the metal salt (D) include the methods described in JP-T-2004-525227 and JP-T 2009-504842. For 1,2-cyclohexanedicarboxylate calcium salt, Milliken Chemical, Hyperform HPN-20E (registered trademark, calcium content of 1,2-cyclohexanedicarboxylate: 66% by weight) from Milliken Japan Co., Ltd. It can be obtained.

[Light stabilizer (E)]
The resin composition according to the present invention may contain a light stabilizer (E) (hereinafter also referred to as component (E)).
As the light stabilizer (E), either a low molecular weight substance or an oligomer type high molecular weight light stabilizer may be used. These can be used alone or in combination of two or more.

For example, a mixture containing bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate; 2,6,6-tetramethyl-4-piperidyl) sebacate;
A reaction product of decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester, 1,1-dimethylethyl hydroperoxide and octane, and bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate;
An ester mixture of 2,2,6,6-tetramethyl-4-piperidinol and a higher fatty acid, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine;
Polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, tetrakis (2,2,6,6-tetra-methyl-4-piperidyl) -1, 2,3,4-butanetetracarboxylate and tetrakis (1,2,2,6,6-penta-methyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate;
Dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6, 6-tetramethyl-4-piperidyl) butylamine and a poly [{(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4- Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}};
N, N ′, N ″, N ″ ″-tetrakis- (4,6bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine -2-yl) -4,7-diazadecane-1,10-diamine and mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetra Methyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethyl} -1,2,3,4-butanetetracarboxylate;
Etc.

  Preferably, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and Reaction product of 1,1-dimethylethyl hydroperoxide and octane, tetrakis (2,2,6,6-tetra-methyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis ( 1,2,2,6,6-penta-methyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, decanedioic acid bis (2,2,6,6-tetramethyl-1 ( Octyloxy) -4-piperidyl) ester, 1,1-dimethylethyl hydroperoxide and octane, dimethyl succinate and 4-hydroxy-2,2,6,6- Polycondensate with tramethyl-1-piperidineethanol, poly [{(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) {(2 , 2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}}.

[Resin composition]
The resin composition according to the present invention contains the component (A), the component (B), the component (C), and the component (D). The content of each component is 50 to 98% by weight, preferably 55 to 82% by weight, of the component (A). The content of the component (B) is 1 to 40% by weight, preferably 10 to 40% by weight. The content of the component (C) is 1 to 30% by weight, preferably 8 to 22% by weight. (However, the total amount of (A), (B) and (C) is 100% by weight).
And content of (D) component is 0.001-1.0 weight part with respect to 100 weight part of total amounts of (A) component, (B) component, and (C) component, Preferably it is 0.01 It is -0.7 weight part, More preferably, it is 0.05-0.5 weight part.
Moreover, content of (E) component is 0.01-1 weight part with respect to 100 weight part of total amounts of (A) component, (B) component, and (C) component, Preferably 0.01- 0.5 parts by weight.

  The melt flow rate measured at 230 ° C. of the resin composition according to the present invention is preferably 0.1 to 400 g / 10 minutes, more preferably 0.5 to 300 g / 10, from the viewpoint of moldability. Minute, more preferably 1 to 200 g / 10 minutes.

  The resin composition of the present invention is obtained by melt-kneading each raw material component at 180 ° C. or higher, preferably 180 to 300 ° C., more preferably 180 to 250 ° C. Examples of the melt kneading include a Banbury mixer, a single screw extruder, a twin-screw co-rotating extruder, and the like.

  Examples of the shape of the resin composition include a strand shape, a sheet shape, a flat plate shape, and a pellet shape obtained by cutting a strand into an appropriate length. In order to mold the resin composition of the present invention, the shape is preferably a pellet having a length of 1 to 50 mm from the viewpoint of production stability of the obtained molded body.

The kneading order of the raw material components is not particularly limited, but the metal salt (D) is preferably blended and kneaded by the following method.
Method 1: Method of blending with (A) component, (B) component, and (C) component Method 2: At least one of (A) component, (B) component, and (C) component, and (D ) A method in which an ingredient is a master batch and this master batch is mixed with the remaining ingredients.

Further, the resin composition of the present invention is a fish generated on the surface of a molded body (film, sheet, injection molded body, etc.) from the viewpoint of impact resistance and appearance of a molded body obtained by molding the resin composition. It is preferable that the generation of eyes (dotted protrusions or dents) is small.
Then, when manufacturing a resin composition in order to suppress generation | occurrence | production of a fish eye, it is preferable to pass a filter after melt-kneading each component. The filter may be single stage or multistage.

  The resin composition according to the present invention may contain a known additive. Examples of additives include neutralizers, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, antiblocking agents, processing aids, organic peroxides, colorants (inorganic pigments, organic pigments, pigment dispersions) Agents), foaming agents, foam nucleating agents, nucleating agents (excluding metal salts (D)), plasticizers, flame retardants, crosslinking agents, crosslinking aids, brightening agents, antibacterial agents, light diffusing agents, inorganic Examples thereof include fillers and anti-scratch agents. These additives may be used alone or in combination of two or more.

  Examples of the neutralizing agent include higher fatty acid metal salts (metal soaps), hydrotalcite, oxides or hydroxides of alkaline earth metals. These neutralizing agents may be used independently and may use 2 or more types together.

  As a higher fatty acid which comprises the metal salt (metal soap) of a higher fatty acid, for example, those having 10 to 30 carbon atoms are preferable, and those having 12 to 18 carbon atoms are more preferable. As the metal salt, for example, calcium salt, sodium salt, magnesium salt, lithium salt, aluminum salt, and zinc salt are preferable, and calcium salt is more preferable. Preferably, it is a calcium salt of stearic acid.

  The hydrotalcite may be a natural mineral or a synthetic product, and its crystal structure, crystal particle diameter, water content, etc. may be appropriately determined. Moreover, you may surface-treat hydrotalcite as needed.

Of the hydrotalcites, hydrotalcites represented by the following formula are preferred.
_{Mg Y Al 2 (OH) 2Y} + 4 CO 3 · mH 2 O
(In the formula, Y is Y ≧ 4, and m is a positive number.)
Further, as hydrotalcites, the following hydrotalcites are more preferable.
_{Mg 4.5 Al 2 (OH) 13} CO 3 · 3H 2 O
Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) _0.8 · O _{0.2
Mg 4 Al 2 (OH) 12} CO 3 · 3H 2 O
Mg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ O
Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O
Zn ₄ Al ₂ (OH) ₁₂ CO ₃ .mH ₂ O (m is 0 to 4)
Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ · mH ₂ O (m is 0 to 4)

  The alkaline earth metal oxide or hydroxide is an oxide or hydroxide of a metal atom belonging to Group 2 of the periodic table, and examples thereof include calcium oxide, magnesium oxide, calcium hydroxide, and magnesium hydroxide. . Preferably it is calcium hydroxide.

  The blending amount of the neutralizing agent is 0.001 to 0.5 parts by weight, preferably 0.005 to 0 with respect to 100 parts by weight of the total amount of the components (A), (B) and (C). 0.5 part by weight, more preferably 0.01 to 0.2 part by weight.

Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hydroxylamine antioxidants, metal deactivators, and the like.
Preferable are a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.
The blending amount of the antioxidant is 0.01 to 2 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the total amount of the components (A), (B) and (C). More preferably, it is 0.01 to 0.5 part by weight.

  Examples of the phenolic antioxidant include 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-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane, triethylene glycol-N-bis-3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis-diethylenebis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], tocopherols and the like.

  Examples of the phosphorus-based antioxidant include tris (2,4-di-t-butylphenyl) phosphite and bis (2,4-di-t-butylphenyl) from the viewpoint of processing stability of the resin composition. Pentaerythritol diphosphite, 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [ 1,3,2] dioxaphosphine and the like.

Examples of the sulfur-based antioxidant include dimyristyl-3,3′-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), and bis [from the viewpoint of heat aging resistance of the resin composition. 2-methyl -4- (3-n- alkyl _(C 12 _{~C 14)} thio propionyloxy) -5-t-butylphenyl] sulfide. C ₁₂ represents ₁₂ carbon atoms, and C ₁₄ represents 14 carbon atoms.

  Examples of the ultraviolet absorber include 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, lauryl 3,5-di-t-butyl-4-hydroxy. Benzoate, palmityl 3,5-di-t-butyl-4-hydroxybenzoate, stearyl 3,5-di-t-butyl-4-hydroxybenzoate, behenyl 3,5-di-t-butyl-4-hydroxybenzoate, etc. Is mentioned.

  Examples of the colorant include inorganic pigments and organic pigments. Examples of the inorganic pigment include iron oxide, titanium oxide, zinc oxide, dial, cadmium red, cadmium yellow, ultramarine blue, cobalt blue, titanium yellow, lead white, red lead, lead yellow, and bitumen. Examples of the pigment include quinacridone, polyazo yellow, anthraquinone yellow, polyazo red, azo lake yellow, perylene, phthalocyanine green, phthalocyanine blue, and isoindolinone yellow. These colorants may be used alone or in combination of two or more. In addition, a pigment and a pigment dispersant may be used in combination for the purpose of dispersing the pigment in the resin composition.

Moreover, the resin composition which concerns on this invention may contain resin and rubber | gum other than the said (A) component, (B) component, (C) component, and (D) component.
For example, polystyrene resin, 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, acrylic resin, ethylene / vinyl alcohol copolymer resin, fluorine resin, polyacetal, polyphenylene ether resin, polyurethane, polyamide, polyester resin, polycarbonate, polysulfone, polyether ether ketone, polyether sulfone Thermoplastic resins such as aromatic polyester resin, epoxy resin, diallyl phthalate prepolymer, silicone resin, silicone rubber, polybutadiene, 1,2-poly Butadiene, polyisoprene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, epichlorohydrin rubber, acrylic rubber, natural rubber, and the like.
Moreover, the resin composition of this invention may contain the polymer manufactured by superposing | polymerizing the plant-derived monomer extracted from the bio raw material. For example, PLA resin (polylactic acid), PBT resin, etc. are mentioned.

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.
Examples of the molded body include automobile materials, home appliance materials, monitor materials, OA equipment materials, medical materials, drain pans, toiletry materials, bottles, containers, sheets, films, building materials, and the like.

Hereinafter, the present invention will be described with reference to examples and comparative examples. The propylene polymer, ethylene polymer, inorganic filler, and additive used in Examples and Comparative Examples are shown below.

(1) Propylene polymer (A) (component (A))
(A-1) Propylene homopolymer MFR (230 ° C., 2.16 kg load): 20 g / 10 polarization limiting viscosity ([η]): 1.34 dl / g

(A-2) Propylene homopolymer MFR (230 ° C., 2.16 kg load): 120 g / 10 polarization limiting viscosity ([η]): 0.92 dl / g

(2) Polymer material (block copolymer) comprising polymer component (I) and polymer component (II)
Using a polymerization catalyst obtained by the method described in Example 1 of Japanese Patent Application Laid-Open No. 2004-182981, a liquid phase-gas phase polymerization method was carried out under conditions such that a propylene polymer having the following physical properties was obtained.

(A-3) (propylene)-(propylene-ethylene) copolymer Polymer MFR (230 ° C., 2.16 kg load): 27 g / 10 min Polymer content ethylene content: 7.5 wt%
Intrinsic viscosity of polymerized material ([η] _total ): 1.41 dl / g
[Η] _II / [η] _I = 2.64
Polymer component (I): Propylene homopolymer component Intrinsic viscosity of polymer component (I) ([η] _I ): 1.06 dl / g
Polymer component (II): Propylene-ethylene copolymer component Content of polymer component (II): 20.5% by weight
Ethylene content of polymer component (II): 37.0% by weight
Intrinsic viscosity of polymer component (II) ([η] _II ): 2.8 dl / g

(A-4) (Propylene)-(propylene-ethylene) copolymer MFR of polymerized material (230 ° C., 2.16 kg load): 32 g / 10 min. Ethylene content of polymerized material: 6.5% by weight
Intrinsic viscosity of polymerized material ([η] _total ): 1.64 dl / g
[Η] _II / [η] _I = 5.00
Polymer component (I): Propylene homopolymer component Intrinsic viscosity of polymer component (I) ([η] _I ): 1.00 dl / g
Polymer component (II): Propylene-ethylene copolymer component Content of polymer component (II): 16.0% by weight
Ethylene content of polymer component (II): 34.5% by weight
Intrinsic viscosity of polymer component (II) ([η] _II ): 5.0 dl / g

(A-5) (propylene)-(propylene-ethylene) copolymer MFR of polymerized material (230 ° C., 2.16 kg load): 67 g / 10 min Polymer content of ethylene: 4.0% by weight
Intrinsic viscosity of polymerized material ([η] _total ): 1.45 dl / g
[Η] _II / [η] _I = 5.93
Polymer component (I): Propylene homopolymer component Intrinsic viscosity of polymer component (I) ([η] _I ): 0.86 dl / g
Polymer component (II): Propylene-ethylene copolymer component Content of polymer component (II): 14.0% by weight
Ethylene content of polymer component (II): 30.0% by weight
Intrinsic viscosity of polymer component (II) ([η] _II ): 5.1 dl / g

(2) Ethylene polymer (B) (component (B))
(B-1) Ethylene-1-butene copolymer elastomer (registered trademark) Tuffmer A1050S (manufactured by Mitsui Chemicals, Inc.)
Density: 0.862 (g / cm ³ )
MFR (190 ° C., 2.16 kg load): 1.3 g / 10 min α-olefin: 1-butene

(B-2) Ethylene-1-butene copolymer elastomer (registered trademark) Tuffmer A4050S (manufactured by Mitsui Chemicals, Inc.)
Density: 0.862 (g / cm ³ )
MFR (190 ° C., 2.16 kg load): 3.5 g / 10 min α-olefin: 1-butene

(B-3) Ethylene-1-octene copolymer elastomer (registered trademark) ENGAGE EG8100 (manufactured by Dow Chemical Japan Co., Ltd.)
Density: 0.87 (g / cm ³ )
MFR (190 ° C., 2.16 kg load): 1 g / 10 min α-olefin: 1-octene

(3) Inorganic filler (C) (component (C))
(C-1) Talc (registered trademark) MWHST: Hayashi Kasei average particle size: 4.9 μm

(C-2) Fibrous magnesium oxysulfate (registered trademark) Moss Heidi A: Average fiber diameter made by Ube Materials: 0.5 μm
Average fiber diameter: 10 μm
Aspect ratio: 20

(C-3) Fibrous magnesium oxysulfate master batch 50% by weight of a propylene homopolymer (A-2) and 50% by weight of Mosheidi A (C-2) manufactured by Ube Materials Co., Ltd. are melt-kneaded. Thus, a master batch (C-3) having a Mosheidi A content of 50% by weight was obtained.

(4) Metal salt (D) (component (D))
(D-1) (registered trademark) Hyperform HPN-20E: Chemical name of main component manufactured by Milliken Japan Co., Ltd .: 1,2-cyclohexanedicarboxylate calcium salt CAS Reg. NO. : 491589-22-1
Structural formula of the main component:

主成分の含有量：６６重量％
副成分の化学名：ステアリン酸亜鉛
ＣＡＳ Ｒｅｇ．ＮＯ．：５５７−０５−１
副成分の含有量：３４重量％
ＨＰＮ−２０Ｅの平均粒子径： 主成分の平均粒子径：２．６μｍ
（平均粒子径はレーザー回折式の粒度分布測定器（Ｓｙｍｐａｔｅｃ社製ＨＥＬＯＳ（商品名））を用いて測定した。）

Main component content: 66% by weight
Chemical name of accessory component: Zinc stearate CAS Reg. NO. : 557-05-1
Subcomponent content: 34% by weight
Average particle diameter of HPN-20E: Average particle diameter of main component: 2.6 μm
(The average particle size was measured using a laser diffraction particle size distribution analyzer (HELOS (trade name) manufactured by Sympatec).)

(D-2) (registered trademark) Hyperform HPN-68L: manufactured by Milliken Japan Co., Ltd. Chemical name of main component: disodium = (1R, 2R, 3S, 4S) -bicyclo [2.2.1] heptane- 2,3-dicarboxylate (containing 80% by weight)
Chemical structural formula of the main component:

(D-3) (registered trademark) AL-PTBBA: manufactured by Kyodo Yakuhin Co., Ltd. Chemical name: hydroxy-di (p-tert-butylbenzoic acid) aluminum

(5) Light stabilizer (E) (component (E))
(E-1) (registered trademark) ADK STAB LA52: manufactured by ADEKA Corporation Chemical name: tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (E-2) (registered trademark) TINUVIN770DF: Ciba Japan Co., Ltd. chemical name: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate

(6) Additive (F) ((F) component)
(F-1) Neutralizing agent calcium stearate: manufactured by Kyodo Yakuhin Co., Ltd. (F-2) antioxidant (registered trademark) Sumilizer GA80: manufactured by Sumitomo Chemical Co., Ltd. Chemical name: 3,9-bis [2- ( 3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane

(F-3) Antioxidant (registered trademark) SONGNOX 6260: manufactured by Matsubara Sangyo Co., Ltd. Chemical name: Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (F-4) UV absorber ( (Registered trademark) Sumisorb 400: manufactured by Sumitomo Chemical Co., Ltd. Chemical name: 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate (F-5) lubricant (registered trademark) Neutron-S: Nippon Seika Co., Ltd. Chemical name: Erucamide (F-6) Lubricant (registered trademark) Denon SL-12: Maruhishi Oil Chemical Co., Ltd. Chemical name: Oleic acid amide (F -7) Lubricant (registered trademark) Armo wax EBS-P: Chemical name manufactured by Lion Corporation: Ethylene bis-stearic acid amide

The physical properties of the raw material components and the resin composition were measured according to the methods shown below.
(1) Melt flow rate (MFR, unit: g / 10 minutes)
It measured according to the method prescribed | regulated to JIS-K-7210.
Propylene polymer (A): Measurement temperature is 230 ° C., load is 2.16 kg
-Ethylene polymer (B): The measurement temperature is 190 ° C and the load is 2.16 kg.
Resin composition: measurement temperature is 230 ° C., load is 2.16 kg

(2) Density (unit: g / cm ³ )
It measured according to the method prescribed | regulated to JIS-K-7112.

(3) Intrinsic viscosity ([η], unit: dl / g)
Using a Ubbelohde viscometer, reduced viscosities were measured at three concentrations of 0.1, 0.2 and 0.5 g / dl. The intrinsic viscosity was obtained by an extrapolation method in which the reduced viscosity was plotted against the concentration as described above, and the concentration was extrapolated to zero.

Measurement and calculation of ratio of polymer components (I) and (II), intrinsic viscosity ([η] _Total , [η] _I , [η] _II ) Limit of polymer component (I) obtained in the previous polymerization step Viscosity ([η] _I ), ultimate viscosity ([η] _Total ) measured by the method of (2) above of the final polymer after the subsequent polymerization step (total of component (I) and component (II)), final From the content (weight ratio) of the polymer component (II) contained in the polymer, the intrinsic viscosity [η] _II of the polymer component (II) polymerized in the subsequent step is calculated from the following formula. It was.
[Η] _II = ([η] _Total − [η] _I × X _I ) / X _II
[Η] _Total : Intrinsic viscosity (dl / g) of the final polymer after the subsequent polymerization step
[Η] _I : Intrinsic viscosity (dl / g) of the polymer powder extracted from the polymerization tank after the pre-stage polymerization step
X _I : Weight ratio of the component polymerized in the previous step X _II : Weight ratio of the component polymerized in the subsequent step Note that X _I and X _II were obtained from the mass balance at the time of polymerization.

(4) Crystallization rate (half crystallization time T0.5, unit: second)
The measurement was performed using “Diamond DSC” (differential scanning calorimeter) manufactured by PerkinElmer Japan Co., Ltd. Specifically, the resin composition pellets were formed into a film (100 μm) with a compression molding machine to prepare a measurement sample. About 10 mg of the sample prepared in the DSC was set, once heated to 220 ° C. and allowed to stand at 220 ° C. for 5 minutes, the sample was completely dissolved. Thereafter, isothermal crystallization was performed by rapidly cooling to 140 ° C. at a temperature lowering rate of 300 ° C./min. The half crystallization time was measured from the obtained endothermic curve. The shorter the crystallization time, the faster the crystallization speed.

(5) Flexural modulus (FM, unit: MPa)
Using a SE130DU injection molding machine manufactured by Sumitomo Heavy Industries, injection molding was performed at a molding temperature of 220 ° C. and a mold temperature of 50 ° C. to obtain a physical property evaluation test piece (6.4 mm thickness). Based on ASTM D790, the bending elastic modulus at 23 ° C. was measured using the test piece.

(6) Dimensional stability (molding shrinkage, unit: / 1000)
A SE180D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. was used for injection molding under the conditions of a molding temperature of 220 ° C. and a mold cooling temperature of 50 ° C. to produce a rectangular parallelepiped test piece having a length of 400 mm, a width of 100 mm and a thickness of 3 mm. The test piece was allowed to stand for 48 hours under a standard condition of a room temperature of 23 ° C. and a humidity of 50%, and then the length (MD) and the horizontal direction (TD) of the test piece were measured. The molding shrinkage in the vertical direction and the molding shrinkage in the horizontal direction were calculated from the following calculation formulas.
MD molding shrinkage = (400−MD dimension / 400) × 1000
TD molding shrinkage = (100−TD dimension / 100) × 1000)

[Examples 1-6, Comparative Examples 1-4]
The blending ratio of the component (A), the component (B), and the component (C) is as follows (however, (A-1), (A-2), (A-5), (B-1 ) And (C-1) in a total amount of 100% by weight).
Propylene homopolymer (A-1): 9% by weight
Propylene homopolymer (A-2): 15% by weight
(Propylene)-(propylene-ethylene) copolymer (A-5): 36% by weight
Ethylene-1-butene copolymer elastomer (B-1): 30% by weight
Talc (C-1): 10% by weight

The blending ratio of the component (D), the component (E), and the component (F) is as shown in Table 1 below.
Moreover, the blending ratio of (F-1), (F-2), (F-3) and (F-7) among the components (F) is as follows (however, (A-1) , (A-2), (A-5), (B-1) and (C-1) as a total amount of 100 parts by weight).
Neutralizer (F-1): 0.05 parts by weight Antioxidant (F-2): 0.05 parts by weight Antioxidant (F-3): 0.05 parts by weight Lubricant (F-7): 0 .03 parts by weight After these were uniformly premixed with a tumbler, using a twin-screw kneading extruder (TEX44αII-49BW-3V type manufactured by Nippon Steel Works), the extrusion rate was 50 kg / hr, the cylinder set temperature was 200 ° C., the screw A resin composition was produced by kneading and extruding at 200 rpm under a vent suction.
The physical properties of the obtained resin composition are shown in Table 1 below.

[Examples 7 to 9, Comparative Example 5]
The blending ratio of the component (A), the component (B), and the component (C) is as follows (however, (A-4), (B-1), (C-1) and (C-3) ) Is 100% by weight).
(Propylene)-(propylene-ethylene) copolymer (A-4): 65% by weight
Ethylene-1-butene copolymer elastomer (B-1): 19% by weight,
Talc (C-1): 4% by weight
Fibrous magnesium oxysulfate master batch (C-3): 12% by weight

The blending ratio of the component (D) is as shown in Table 2 below.
Moreover, the blending ratio of the component (E) and the component (F) is as follows (however, the total amount of (A-4), (B-1), (C-1) and (C-3)) Is 100 parts by weight).
Neutralizer (F-1): 0.05 parts by weight Antioxidant (F-2): 0.05 parts by weight Antioxidant (F-3): 0.05 parts by weight Lubricant (F-7): 0 0.03 part by weight light stabilizer (E-1): 0.1 part by weight UV absorber (F-4): 0.2 part by weight Lubricant (F-5): 0.15 part by weight After premixing, using a twin-screw kneading extruder (TEX44αII-49BW-3V type manufactured by Nippon Steel Co., Ltd.), the extrusion rate is 50 kg / hr, the cylinder set temperature is 200 ° C., the screw rotation speed is 200 rpm, and the mixture is kneaded under vent suction. The resin composition was manufactured by extrusion.
The physical properties of the obtained resin composition are shown in Table 2 below.

[Example 10, Comparative Example 6]
The blending ratio of the component (A), the component (B), and the component (C) is as follows (however, the total amount of (A-3), (B-2), and (C-1) is 100). %).
(Propylene)-(propylene-ethylene) copolymer (A-3): 70.5% by weight
Ethylene-1-butene copolymer elastomer (B-2): 8% by weight
Talc (C-1): 21.5% by weight

The blending ratio of component (D) is as shown in Table 3 below.
Moreover, the mixture ratio of (F) component is as follows (however, the total amount of (A-3), (B-2), and (C-1) is 100 weight part).
Neutralizer (F-1): 0.05 parts by weight Antioxidant (F-2): 0.05 parts by weight Antioxidant (F-3): 0.05 parts by weight Lubricant (F-7): 0 .07 parts by weight After these were uniformly premixed with a tumbler, using a twin-screw kneading extruder (TEX44αII-49BW-3V type manufactured by Nippon Steel Works), the extrusion rate was 50 kg / hr, the cylinder set temperature was 200 ° C., the screw A resin composition was produced by kneading and extruding at 200 rpm under a vent suction.
The physical properties of the obtained resin composition are shown in Table 3 below.

[Example 11, Comparative Examples 7 to 9]
The blending ratio of the component (A), the component (B), and the component (C) is as follows (however, (A-1), (A-2), (A-5), (B-3 ) And (C-1) in a total amount of 100% by weight).
Propylene homopolymer (A-1): 9% by weight
Propylene homopolymer (A-2): 15% by weight
(Propylene)-(propylene-ethylene) copolymer (A-5): 36% by weight
Ethylene-1-octene copolymer elastomer (B-3): 30% by weight
Talc (C-1): 10% by weight

The blending ratio of component (D) is as shown in Table 4 below.
The blending ratio of the component (E) and the component (F) is as follows (however, (A-1), (A-2), (A-5), (B-3) and (C -1) is 100 parts by weight).
Light stabilizer (E-1): 0.1 parts by weight Neutralizer (F-1): 0.05 parts by weight Antioxidant (F-2): 0.05 parts by weight Antioxidant (F-3) : 0.05 parts by weight lubricant (F-6): 0.2 parts by weight lubricant (F-7): 0.03 parts by weight After these were uniformly premixed with a tumbler, a twin-screw kneading extruder (Nippon Steel Works) Using a TEX44αII-49BW-3V type), a resin composition was produced by kneading and extruding at an extrusion rate of 50 kg / hr, a cylinder set temperature of 200 ° C., a screw rotation speed of 200 rpm, and vent suction.
The physical properties of the obtained resin composition are shown in Table 4 below.

Claims (4)

Propylene polymer (A) and 50 to 98 wt%, and the ethylene polymer (B) 1 to 40 wt% of the density of 0.85~0.93 (g / cm ^3), talc and / or a fibrous inorganic filler Inorganic filler (C) 8-30 wt% as a material (the total weight of (A), (B) and (C) is 100 wt%)
Inclusive of 0.001 to 1.0 part by weight of at least one metal salt (D) represented by the following general formula (I) with respect to 100 parts by weight of the total amount of (A), (B) and (C). Polypropylene resin composition.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, 1 to 9 carbon atoms] An alkyl group, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, a halogen atom, a phenyl group and any group selected from the group consisting of the following general formulas (II) and (III). Here, when at least two groups adjacent to each other among these groups are alkyl groups, these alkyl groups may be bonded to each other to form a carbocyclic ring having up to 6 carbon atoms. R ¹ and R ² of this compound are in cis configuration. ]
^{- (R 11 O) n-} X ··· (II)
[Wherein R ¹¹ represents an alkylene group having 1 to 9 carbon atoms, n represents an integer of 1 to 9, X represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a benzoyl group, The phenyl group substituted by the phenyl group, the C1-C9 alkyl group, and / or the halogen atom is represented. ]
-NR ¹² R ¹³ (III)
[Wherein, R ¹² and R ¹³ are each independently a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 9 carbon atoms. ]   The polypropylene resin composition according to claim 1, further comprising 0.01 to 1.0 parts by weight of a light stabilizer (E) with respect to 100 parts by weight of the total amount of (A), (B) and (C). . The polypropylene resin composition according to claim 1 or 2, wherein the metal salt (D) is a cis-1,2-cyclohexanedicarboxylate calcium salt represented by the following structural formula.

Molded article comprising the polypropylene resin composition according to any one of claims 1 to 3.