JP6916713B2 - Polypropylene resin composition and molded product - Google Patents

Description

The present invention relates to polypropylene-based resin compositions and molded articles.

Polypropylene-based resin compositions containing polypropylene as a main component are used in various applications because they are inexpensive and have excellent mechanical properties such as rigidity. Since polypropylene-based resin compositions containing rubber components such as elastomers are also excellent in impact resistance, they are widely used in various fields such as automobile interior materials, daily necessities, and housings for electric appliances. When these molded products are produced by an injection molding method, the polypropylene-based resin composition is required to have appropriate fluidity during molding. Further, in the field of automobile interior materials, it may be required not only to improve the physical property balance (rigidity, impact resistance, etc.) of the molded body, but also to reduce the gloss of the surface of the molded body for the purpose of improving the appearance.

Patent Document 1 specifies as a molded product made of a polypropylene-based resin composition having excellent physical property balance such as rigidity and impact resistance and appearance performance such as flow mark (tiger mark), as well as low gloss and scratch resistance. An automobile interior molded article containing an ethylene / propylene copolymer, an ethylene / α-olefin copolymer, and an inorganic filler is disclosed. Further, in Patent Document 2, a molded product obtained by molding the composition can be used as an interior material of an automobile, and a resin composition excellent in balance between rigidity and impact resistance of the molded product, low gloss and scratch resistance. As a product, a polypropylene-based resin composition characterized by containing a specific polypropylene-based resin, an ethylene / α-olefin copolymer, and an inorganic filler is disclosed.

Japanese Patent No. 4041705 Japanese Unexamined Patent Publication No. 2015-124272

In Patent Document 1, the specific gravity of the molded product, that is, the weight is not examined at all. In Patent Document 2, the inorganic filler contained in the polypropylene-based resin composition is 15 to 30 parts by weight, but the specific gravity of the molded product obtained by molding the resin composition thus obtained is approximately 1.0. It exceeds, and it is not necessarily low specific gravity. In order to improve the fuel efficiency of automobiles, it is of great significance to reduce the specific density (weight reduction) of molded products. It is conceivable to reduce the content of the inorganic filler in order to reduce the specific density of the molded product. However, when the rubber component is contained, if the inorganic filler is easily reduced, the balance of physical properties such as rigidity and impact resistance is lost.
For this reason, a molded product having a low specific density and low gloss, a good balance of physical properties, an appearance in which the tiger mark is suppressed, and excellent scratch resistance, and a polypropylene-based resin capable of molding the molded product, and a polypropylene-based resin capable of molding the molded product. The composition is sought after.

The present invention relates to a molded product having a low specific gravity, excellent rigidity, impact resistance, and scratch resistance, low gloss, and an appearance in which tiger marks are suppressed, and a polypropylene-based resin composition capable of molding the molded product. I will provide a.

The present invention has the following aspects.
[1] Polypropylene resin as component (A), polypropylene resin as component (B), ethylene / α-olefin copolymer as component (C), filler as component (D), (E) It contains a crystal nucleating agent as a component and a higher fatty acid amide as a component (F).
The component (A) is a block polypropylene (A-1) composed of a propylene homopolymer (A-1a) and an ethylene / propylene copolymer (A-1b), and if necessary, according to JIS K6921-2. The melt flow rate (MFR) measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg further contains a propylene homopolymer (A-2) having a melt flow rate (MFR) of 500 to 2000 g / 10 min, and further contains a propylene homopolymer (A-1a) and propylene. The temperature is 230 according to JIS K6921-2, which consists of a total of 75 to 90% by mass of the propylene homopolymer including the homopolymer (A-2) and 10 to 25% by mass of the ethylene / propylene copolymer (A-1b). It is a polypropylene-based resin (A1) having an MFR of 40 to 70 g / 10 min measured under the conditions of ° C. and a load of 2.16 kg.
The ultimate viscosity (XSIV) of the xylene-soluble component of the block polypropylene (A-1) at 25 ° C. is 0.5 to 4.0 dL / g, and is contained in the ethylene-propylene copolymer (A-1b). The ethylene unit content is 20 to 50% by mass,
The component (B) is composed of 60 to 80% by mass of the propylene homopolymer (B-1a) and 20 to 40% by mass of the ethylene / propylene copolymer (B-1b), and has a temperature of 230 according to JIS K6921-2. The MFR measured under the conditions of ° C. and a load of 2.16 kg was 5 to 30 g / 10 min, the Mw / Mn of the xylene insoluble component at 25 ° C. was 6 to 20, and the extreme viscosity of the xylene soluble component at 25 ° C. (XSIV) is a polypropylene-based resin made of block polypropylene having a value of 5.5 to 9.0 dL / g.
The ethylene unit content in the ethylene / propylene copolymer (B-1b) is 20 to 40% by mass.
The component (C) has an α-olefin having 4 to 8 carbon atoms, has a long-chain branch, and has an MFR of 0. It contains the component (C1), which is an elastomer composed of an ethylene / α-olefin copolymer having a density of 1 to 5 g / 10 min and a density of 0.857 to 0.873 g / cm ^3.
When the total mass of the component (A), the component (B), the component (C), and the component (D) is 100% by mass, the content of the component (A) is 45 to 81% by mass. The content of the component (B) is 4 to 20% by mass, the content of the component (C1) is 5 to 20% by mass, and the content of the component (D) is 10% by mass or more. Less than 15% by weight
When the total mass of the component (A), the component (B), the component (C), and the component (D) is 100 parts by mass, the content of the component (E) is 0.05 to 0. .. A polypropylene resin composition having 4 parts by mass and a content of the component (F) of 0.05 to 0.5 parts by mass.
[2] The polypropylene-based resin composition according to [1], wherein the total MFR of the composition is 20 to 35 g / 10 min, measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K6921-2.
[3] The propylene homopolymer (A-2) when the total mass of the component (A), the component (B), the component (C), and the component (D) is 100% by mass. The polypropylene-based resin composition according to [1] or [2], which has a content of 2 to 20% by mass.
[4] A molded product obtained from the polypropylene-based resin composition according to any one of [1] to [3].

According to the polypropylene-based resin composition of the present invention, a molded product having a low specific density, excellent rigidity, impact resistance, and scratch resistance, low gloss, and an appearance in which tiger marks are suppressed can be obtained.

In the present specification, "~" indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

The polypropylene-based resin composition of the present invention (hereinafter, also referred to as "the present resin composition") includes the following component (A), the following component (B), the following component (C), and the following component (D). , The following component (E) and the following component (F) are included.
The present resin composition may further contain components other than the components (A) to (F).

The MFR of the entire composition of the present resin composition is preferably 20 to 35 g / 10 min, more preferably 20 to 30 g / 10 min. When the MFR of the entire composition is at least the lower limit of the above range, the fluidity at the molding temperature of injection molding (for example, 200 to 240 ° C.) is sufficiently high, and it can be used as a material that is easy to injection mold. When the MFR of the entire composition is not more than the upper limit of the above range, the physical property balance (particularly impact resistance) of the molded product is excellent.
The MFR of the entire composition is a value measured according to JIS K6921-2 under the conditions of a temperature of 230 ° C. and a load of 2.16 kg.
The MFR of the entire composition can be adjusted by the respective contents of the components (A) to (F), the MFR of the components (A) to (C), and the like.

<Ingredient (A)>
The component (A) is a base material component of the present resin composition. The component (A) in the present invention is a polypropylene-based resin (A1) that satisfies the following (i) to (iv).
(I) Contains block polypropylene (A-1) composed of a propylene homopolymer (A-1a) and an ethylene / propylene copolymer (A-1b). The propylene homopolymer (A-2) described later may be contained. A total of 75 to 90% by mass of the propylene homopolymer composed of the propylene homopolymer (A-1a) and the propylene homopolymer (A-2) which may be optionally contained, and the ethylene / propylene copolymer (A-1b). It consists of 10 to 25% by mass.
(Ii) According to JIS K6921-2, the MFR measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg is 40 to 70 g / 10 min.
The ultimate viscosity (XSIV) of the xylene-soluble component of (iii) block polypropylene (A-1) at 25 ° C. is 0.5 to 4.0 dL / g.
(Iv) The ethylene unit content (ethylene unit content ratio) in the ethylene / propylene copolymer (A-1b), that is, the ethylene unit content with respect to the total mass of the ethylene / propylene copolymer (A-1b). It is 20 to 50% by mass.

Polypropylene composed of a propylene homopolymer component and an ethylene / propylene copolymer component includes heterophasic polypropylene, heterophasic polypropylene, impact-resistant propylene polymer, impact-resistant polypropylene polymer, or block polypropylene. It is a kind of polypropylene-based resin called. The ethylene / propylene copolymer component is an elastomer component.

Block polypropylene (A-1) is a chemical bond of a propylene homopolymer component (A-1a) and an ethylene / propylene copolymer component (A-1b). It may be a mere blend of a propylene homopolymer (A-1a) and an ethylene / propylene copolymer (A-1b).
Block polypropylene (A-1) can be obtained by polymerizing ethylene and propylene in the presence of a propylene homopolymer component. The method for producing the component (A) will be described in detail later.

The propylene homopolymer component is typically crystalline homopolypropylene.
The crystalline homopolypropylene is a homopolypropylene having high stereoregularity, and is 150 to 170 ° C., preferably 155 ° C. when measured by DSC (differential scanning calorimetry) at a heating rate of 10 ° C./min based on JIS K7121. Homopolypropylene with a main melting peak observed at ~ 170 ° C. The propylene homopolymer component may contain a monomer unit other than propylene in an amount of less than 0.5% by mass due to the recycled gas generated during the production of the polymer containing the copolymer component.

The ethylene / propylene copolymer component consists of an ethylene unit and a propylene unit.
The ethylene unit content in the ethylene / propylene copolymer (A-1b) is 20 to 50% by mass, and 25 to 50% by mass, based on the total mass of the ethylene / propylene copolymer (A-1b). preferable. When the ethylene unit content is within the above range, the impact resistance of the molded product is excellent.
The ethylene unit content is ^{measured by the 13} C-NMR (Nuclear Magnetic Resonance) method.

The content of the ethylene-propylene copolymer (A-1b) in the block polypropylene (A-1) or in the mixture of the block polypropylene (A-1) and the propylene homopolymer (A-2) described later (hereinafter). The "BIPO amount") is 10 to 25% by mass, preferably 12 to 22% by mass, more preferably 15 to 20% by mass, based on the total mass of the block polypropylene (A-1) or the mixture. .. When the amount of BIPO is at least the lower limit of the above range, the impact resistance of the molded product is excellent. When the amount of BIPO is not more than the upper limit of the above range, the rigidity of the molded product is excellent.
The amount of BIPO is ^{measured by the 13} C-NMR method.
The content of the propylene homopolymer (A-1a) in the block polypropylene (A-1) or in the mixture of the block polypropylene (A-1) and the propylene homopolymer (A-2) described later. Alternatively, the total content of the propylene homopolymer (A-1a) and the propylene homopolymer (A-2) is the total mass of the block polypropylene (A-1) or the block polypropylene (A-1) and the propylene alone. It is obtained by subtracting the amount of BIPO from the total mass of the mixture with the polymer (A-2).

The ultimate viscosity of the xylene-soluble component of block polypropylene (A-1) at 25 ° C. (hereinafter, also referred to as “XSIV”) is 0.5 to 4.0 dL / g, and 1.0 to 3.5 dL / g. g is preferable, and 1.5 to 3.0 dL / g is more preferable. XSIV can be regarded as the ultimate viscosity of the ethylene / propylene copolymer component in the block polypropylene (A-1). When XSIV is at least the lower limit of the above range, the tiger mark can be suppressed and the increase in gloss can be suppressed. When XSIV is not more than the upper limit of the above range, the impact resistance is excellent.
XSIV is a measured value in tetrahydronaphthalene at 135 ° C.

The optional component propylene homopolymer (A-2) is a crystalline homopolypropylene. The propylene homopolymer (A-2) is a high-flow crystalline polypropylene having an MFR of 500 to 2000 g / 10 min measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K6921-2. The MFR of the propylene homopolymer (A-2) can be prepared by its molecular weight, and its molecular weight can be prepared by the hydrogen concentration at the time of polymerization.

The MFR of the component (A1) is 40 to 70 g / 10 min, more preferably 45 to 60 g / 10 min. When the MFR of the component (A) is equal to or higher than the lower limit of the above range, the MFR of the present resin composition is set to be equal to or higher than the lower limit of the above range, and injection molding becomes easy. When the MFR of the component (A) is not more than the upper limit of the above range, the impact resistance of the molded product is excellent.
The MFR of the component (A) can be adjusted by the MFR of the block polypropylene (A-1), the MFR of the propylene homopolymer (A-2) which is an optional component, the content, and the like. The MFR of block polypropylene (A-1) can be adjusted by the content of the ethylene-propylene copolymer (A-1b), the molecular weight of the propylene homopolymer (A-1a), and the like. The molecular weights of the propylene homopolymer (A-1a) and the propylene homopolymer (A-2) can be adjusted by the hydrogen concentration at the time of polymerization.

<Ingredient (B)>
The component (B) is a polypropylene resin satisfying the following (vi) to (x). The component (B) contributes to the suppression of the tiger mark on the molded product.
(Vi) It is composed of 60 to 80% by mass of the propylene homopolymer (B-1a) and 20 to 40% by mass of the ethylene / propylene copolymer (B-1b).
(Vii) According to JIS K6921-2, the MFR measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg is 5 to 30 g / 10 min.
(Viii) The Mw / Mn of the xylene insoluble matter at 25 ° C. is 6 to 20.
(IX) The ultimate viscosity (XSIV) of the xylene-soluble component at 25 ° C. is 5.5 to 9.0 dL / g.
(X) The ethylene unit content in the ethylene / propylene copolymer (B-1b), that is, the ethylene unit content with respect to the total mass of the ethylene / propylene copolymer (B-1b) is 20 to 40% by mass. ..

The component (B) may be a chemically bonded propylene homopolymer (B-1a) which is a crystalline homopolypropylene and an ethylene / propylene copolymer (B-1b), and propylene alone. It may be a simple blend of the polymer (B-1a) and the ethylene / propylene copolymer (B-1b).
The component (B) is obtained by polymerizing ethylene and propylene, and if necessary, other monomers in the presence of a propylene homopolymer. The method for producing the component (B) will be described in detail later.

The ethylene / propylene copolymer component consists of an ethylene unit and a propylene unit.
The ethylene unit content in the ethylene / propylene copolymer (B-1b) is 20 to 40% by mass with respect to the total mass of the ethylene / propylene copolymer (B-1b), and 25 to 35% by mass. preferable. When the ethylene unit content is within the above range, the impact resistance of the molded product and the effect of suppressing the tiger mark are excellent.
The ethylene unit content is ^{measured by the 13} C-NMR (Nuclear Magnetic Resonance) method.

The content (BIPO amount) of the ethylene-propylene copolymer (B-1b) in the component (B) is 20 to 40% by mass with respect to the total mass of the component (B), and 25 to 35% by mass. preferable. When the amount of BIPO is at least the lower limit of the above range, the impact resistance of the molded product is excellent. When the amount of BIPO is not more than the upper limit of the above range, the rigidity of the molded product and the productivity at the time of manufacturing are excellent.
The amount of BIPO is ^{measured by the 13} C-NMR method.
The content of the propylene homopolymer (B-1a) in the component (B) is obtained by subtracting the amount of BIPO from the total mass of the component (B).

The MFR of the component (B) is 5 to 30 g / 10 min, preferably 6 to 20 g / 10 min, and more preferably 6 to 15 g / 10 min. When the MFR of the component (B) is at least the lower limit of the above range, the MFR of the present resin composition is likely to be at least the lower limit of the above range, and injection molding is facilitated. When the MFR of the component (B) is not more than the upper limit of the above range, the impact resistance of the molded product is excellent.
The MFR of the component (B) can be adjusted by the amount of BIPO, the molecular weight of the propylene homopolymer (B-1a), and the like. The molecular weight of the propylene homopolymer (B-1a) can be adjusted by the hydrogen concentration at the time of polymerization.

The Mw / Mn of the xylene insoluble component of the component (B) at 25 ° C. is 6 to 20, preferably 7 to 20, more preferably 8 to 20, and even more preferably 9 to 20. The xylene-insoluble Mw / Mn can be regarded as the molecular weight distribution of the propylene homopolymer component in the block polypropylene (B). When Mw / Mn is at least the lower limit of the above range, the tiger mark of the molded product can be suppressed and the fluidity of the composition is improved. When Mw / Mn is not more than the upper limit of the above range, the component (B) can be easily produced or obtained.
For the Mw / Mn of the xylene insoluble component of the component (B) at 25 ° C., the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography, and Mw / Mn was calculated. This is the value obtained.

The intrinsic viscosity (XSIV) of the xylene-soluble component of the component (B) at 25 ° C. is 5.5 to 9.0 dL / g, preferably 6.0 to 8.0 dL / g. The XSIV of the component (B) can be regarded as the ultimate viscosity of the ethylene / propylene copolymer component in the component (B). When XSIV is at least the lower limit of the above range, the tiger mark can be suppressed and the increase in gloss can be suppressed. When XSIV is not more than the upper limit of the above range, the impact resistance is excellent.
XSIV is a measured value in tetrahydronaphthalene at 135 ° C.

<Ingredient (C)>
The component (C) is an elastomer component composed of an ethylene / α-olefin copolymer. The component (C) in the present invention contains an elastomer (C1) that satisfies the following (xii) to (xv). The component (C1) satisfying (xii) to (xv) contributes to the reduction of the gloss of the molded product and the improvement of the impact resistance.
(Xii) An ethylene / α-olefin copolymer having 4 to 8 carbon atoms of the α-olefin.
(Xiii) It has a long-chain branch (lоng-chain branch).
(Xiv) According to JIS K6922-2, the MFR measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 5 g / 10 min.
The (xv) density is 0.857 to 0.873 g / cm ³ .

The ethylene / α-olefin copolymer has an ethylene unit and an α-olefin unit having 4 to 8 carbon atoms.
Examples of the α-olefin having 4 to 8 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene and the like, and 1-butene is preferable.
The ethylene / α-olefin copolymer may further have a monomer unit other than the ethylene unit and the α-olefin unit as long as the original characteristics of the ethylene / α-olefin copolymer are not impaired. Examples of other monomers include diene and the like.

"Long chain branching" means a high molecular weight branched chain extending from a high molecular weight molecular chain (main chain). Therefore, the molecular chain of the component (C1) is a branched molecular chain having at least one branch point.
Each of the "main chain" and the "branched chain" is a part composed of a plurality of structural units (monomer units).
The main chain and the branched chain of the component (C1) each have an ethylene unit and an α-olefin unit having 4 to 8 carbon atoms. Further, the constituent unit composition of the main chain and the constituent unit composition of the branched chain are the same.
When the longest linear molecular chain in the component (C1) is used as the main chain, the number of long chain branches extending from the main chain is typically 1 to 5 per 10,000 carbon atoms in the main chain. Degree.

The presence or absence of long-chain branches and the number of long-chain branches affect the dynamic viscosity. When the ethylene / α-olefin copolymer is linear and has a long-chain branch, the one having a long-chain branch has a dynamic viscosity in a low shear rate region of about ^{0.1 to 1 sec -1.} Increases, and the dynamic viscosity in the high shear rate region near 10 to 100 sec ^{-1 decreases.} Further, in the case of having long chain branches, the larger the number of long chain branches, the higher the dynamic viscosity in the low shear rate region and the lower the dynamic viscosity in the high shear rate region. Further, the slower the shear rate in the low shear rate region or the faster the shear rate in the high shear rate region, the more remarkable the difference in dynamic viscosity becomes.
Therefore, an ethylene / α-olefin copolymer having a known structure (a linear ethylene / α-olefin copolymer, an ethylene / α-olefin copolymer having a plurality of long-chain branches having different numbers of long-chain branches) is obtained in advance. ), By creating a graph showing the relationship between the shear rate and the dynamic viscosity, the presence or absence of long-chain branches and the number of long-chain branches can be determined even for ethylene / α-olefin copolymers of unknown structure. can. Alternatively, the presence or absence of long-chain branches and the number of long-chain branches can be confirmed by methods such as strain hardening in extensional viscosity measurement and observation of differences in molecular spread by GPC / LS (gel permeation chromatography / light scattering) measurement.

Since the ethylene / α-olefin copolymer having a long chain branch has a high melt tension, it is possible to reduce the gloss of the molded product in injection molding.

The MFR of the component (C1) is 0.1 to 5 g / 10 min, preferably 0.3 to 3 g / 10 min. When the MFR of the component (C1) is equal to or higher than the lower limit of the above range, the MFR of the present resin composition is likely to be equal to or higher than the lower limit of the above range. When the MFR of the component (C1) is not more than the upper limit of the above range, the balance of physical properties such as rigidity and impact resistance is excellent, and the gloss of the molded product can be reduced.

The density of the component (C1) is a ^{0.857~0.873g / cm 3, 0.858~0.865g / cm} 3 are preferred. When the density of the component (C1) is equal to or higher than the lower limit of the above range, the component (C1) can be easily produced or obtained. When the density of the component (C1) is not more than the upper limit of the above range, the impact resistance of the molded product is excellent and the gloss of the molded product can be reduced.
Density is measured according to the underwater replacement method specified in JIS K7112.

<Ingredient (D)>
The component (D) is a filler and is added mainly for the purpose of improving the rigidity of the molded product. Natural silicic acids or silicates such as talc, kaolinite, calcined clay, bilophyllite, cerinite, wollastonite; carbonates such as precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate; aluminum hydroxide, magnesium hydroxide Hydroxide such as; oxide such as zinc oxide and magnesium oxide; and synthetic silicate such as hydrous calcium carbonate, hydrous aluminum silicate, hydrous silicic acid, powdered filler such as silicate, and flakes such as mica. Fillers; Fibrous fillers such as basic magnesium sulfate whisker, calcium carbonate whisker, aluminum borate whisker, sepiolite, PMF (Proceeded Mineral Filler), zonotrite, potassium titanate, and elestadite; as well as glass balun, fly ash balun Examples thereof include a balun-like filler such as, an inorganic filler such as glass fiber, and an organic filler such as carbon fiber and cellulose fiber. In order to improve the dispersibility of these fillers, the surface treatment of the filler and the compounding of the filler and the resin (preparation of a masterbatch) may be performed, if necessary. Among the fillers, talc is preferable because it has good dispersibility in the present resin composition, easily improves the rigidity of the molded product, and easily reduces the gloss of the molded product. As the filler, one type may be used alone, or two or more types may be used in combination.

<Ingredient (E)>
The component (E) is a crystal nucleating agent, and is an additive (rigid nucleating agent) used for controlling the crystallinity in the resin and increasing the rigidity of the molded product. Since it promotes cooling and solidification of the molten resin, it can be used for the purpose of shortening the cycle time in a molding process such as injection molding, in addition to imparting rigidity.
The crystal nucleating agent is not particularly limited, and those usually used in the art may be used, but a phosphoric acid ester-based nucleating agent, a nonitol-based nucleating agent, a sorbitol-based nucleating agent, a triaminobenzene derivative nucleating agent, and a carboxylic acid. It is preferable to select from a metal salt nucleating agent and an organic crystal nucleating agent such as a xylitol-based nucleating agent or a rosin-based nucleating agent, and a phosphoric acid ester-based nucleating agent is particularly preferable.

Examples of the phosphoric acid ester-based nucleating agent include phosphoric acid 2,2'-methylenebis (4,6-di-t-butylphenyl) sodium salt and phosphoric acid-2,2'-methylenebis (4,6-di-tert). Examples thereof include aromatic phosphate ester-based nucleating agents such as −butylphenyl) aluminum salt and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) lithium salt.
Examples of the nonitol-based nucleating agent include 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol. Examples of the sorbitol-based nucleating agent include 1,3: 2,4-bis-o- (3,4-dimethylbenzylidene) -D-sorbitol.
Examples of the triaminobenzene derivative-based nucleating agent include 1,3,5-tris (2,2-dimethylpropanamide) benzene.
Examples of the metal carboxylate nucleating agent include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate, and diparat-butyl. Examples thereof include aluminum benzoate, titanium di-para-t-butyl benzoate, chromium di-para-t-butyl benzoate, and aluminum hydroxy-di-t-butyl benzoate.
Examples of xylitol-based nucleating agents include bis-1,3: 2,4- (5', 6', 7', 8'-tetrahydro-2-naphthaldehydebenzylidene) 1-allylxylitol, bis-1,3: 2,4- (3', 4'-dimethylbenzylidene) 1-propylxylitol can be mentioned.
Rosin-based nucleating agents include pimaric acid, sandalacopimaric acid, palastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoavietic acid, dihydropimal acid, dihydroabietic acid, tetrahydroabietic acid and other logic acids, and calcium and magnesium. It is a rosinic acid metal salt compound or a rosinic acid partial metal salt compound obtained by a reaction with a metal such as rosinate, and examples thereof include a rosinic acid partial calcium salt.
One type of crystal nucleating agent may be used alone, or two or more types may be used in combination.

<(F) component>
The component (F) is a higher fatty acid amide. The higher fatty acid constituting the higher fatty acid amide may be a saturated fatty acid or an unsaturated fatty acid. The higher fatty acid has 10 or more carbon atoms, preferably 12 or more carbon atoms. Specific higher fatty acid amides include saturated fatty acid amides such as lauric acid amide, palmitate amide, stearic acid amide and behemic acid amide; Saturated fatty acid amides; bis fatty acid amides such as methylene bisstearic acid amides, methylene bistreic acid amides, ethylene bisstearic acid amides, and ethylene bisoleic acid amides can be mentioned. Of these, erucic acid amide, oleic acid amide, and ethylene bisoleic acid amide are preferable.

<Other ingredients>
Other components include, for example, antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, UV absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, antifogging agents, flame retardants, dispersions. Additives such as agents, copper damage inhibitors, neutralizers, plasticizers, foaming agents, bubble inhibitors, cross-linking agents, peroxides, oil spreads and pigments (organic or inorganic) can be mentioned. Further, a resin other than the components (A) to (B) may be contained, or an elastomer component other than the component (C) may be contained for the purpose of improving fluidity and impact resistance as long as the effects of the present invention are not impaired. .. The other components may be only one kind or two or more kinds. The content of other components may be a known amount.

<Contents of each component>
In this resin composition, when the total mass of the component (A), the component (B), the component (C) and the component (D) is 100% by mass, the content of the component (A) is 45 to 81% by mass. , The content of the component (B) is 4 to 20% by mass, the content of the component (C1) contained in the component (C) is 5 to 20% by mass, and the content of the component (D) is 10% by mass or more 15 It is less than% by mass.
Further, when the total mass is 100% by mass, the content of the component (A) is 50 to 79% by mass, the content of the component (B) is 5 to 15% by mass, and the content of the component (C1) is. It is preferable that the content is 5 to 15% by mass and the content of the component (D) is 11 to 14% by mass.
Further, when the total mass is 100% by mass, the content of the component (A) is 55 to 75% by mass, the content of the component (B) is 7 to 13% by mass, and the content of the component (C1) is It is more preferable that the content of the component (D) is 5 to 15% by mass and the content of the component (D) is 11 to 14% by mass.
When the content of the component (A) is equal to or higher than the lower limit of the above range, the fluidity of the resin composition becomes good, injection molding becomes easy, and the impact resistance of the molded product is improved. When the content of the component (A) is not more than the upper limit of the above range, the balance between the rigidity and the impact resistance of the molded product is good. When the content of the component (B) is not less than the lower limit value of the above range, the tiger mark of the molded product is suppressed, and when it is not more than the upper limit value, the fluidity of the present resin composition is excellent and injection molding becomes easy. .. When the content of the component (C1) is at least the lower limit of the above range, the gloss of the molded product is suppressed and the impact resistance is improved. When the content of the component (C1) is not more than the upper limit of the above range, the fluidity of the present resin composition is excellent and injection molding becomes easy. When the content of the component (D) is not less than the lower limit value of the above range, the rigidity of the molded product is improved, and when it is not more than the upper limit value, the tiger mark of the molded product can be suppressed and the increase of the specific gravity can be suppressed.

When the component (A) of the present resin composition contains the propylene homopolymer (A-2), the content of the propylene homopolymer (A-2) is the component (A), the component (B), (C). When the total mass of the component and the component (D) is 100% by mass, it is preferably 2 to 20% by mass, more preferably 3 to 15% by mass, and 3 to 10% by mass. Is even more preferable.
If it is equal to or higher than the lower limit of the above range, the fluidity is excellent. If it is not more than the upper limit of the above range, the impact resistance is excellent.

The content of the component (E) is 0.05 to 0.4 parts by mass with respect to a total of 100 parts by mass of the components (A), (B), (C) and (D), and 0. 1 to 0.3 parts by mass is more preferable. When the content of the component (E) is not less than the lower limit of the above range, the rigidity of the molded product is excellent, and when it is not more than the upper limit of the above range, the manufacturing cost can be suppressed low. Even if the component (E) is contained in excess of the upper limit value, the effect of promoting crystal nucleation reaches a plateau and the production cost simply increases, which is not realistic in the case of industrially mass production at low cost.

The content of the component (F) is 0.05 to 0.5 parts by mass with respect to a total of 100 parts by mass of the components (A), (B), (C) and (D). 1 to 0.4 parts by mass is more preferable, and 0.15 to 0.35 parts by mass is further preferable.
When the content of the component (F) is at least the lower limit of the above range, the scratch resistance of the molded product is excellent, and when it is at least the upper limit of the above range, blooming and odor of the component (F) in the molded product are suppressed. can do.

<Manufacturing method of polypropylene resin composition>
Examples of the method for producing the present resin composition include a method of mixing the component (A), the component (B), the component (C), the component (D), the component (E), and the component (F). If necessary, any one or more of the other components may be further mixed. There is no limitation on the order of addition of each component.
The mixing method is not particularly limited, and examples thereof include a method using a mixer such as a Henschel mixer or a tumbler mixer.
After mixing, the obtained mixture may be melt-kneaded and further pelletized. As the melt-kneading device, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a roll mill, or the like can be used.
As the components (A) to (F) and other components, if a commercially available product is available, a commercially available product may be used. Those manufactured by a known manufacturing method may be used.

(Method for manufacturing component (A))
Examples of the method for producing the block polypropylene (A-1) component include a method of polymerizing ethylene and propylene, and if necessary, other monomers in the presence of the propylene homopolymer (A-1a). The polymerization produces an ethylene / propylene copolymer (A-1b), and a blocked polypropylene (A-1) component is obtained as a polymerization product. This method has high productivity, and further, the dispersibility of the ethylene-propylene copolymer in block polypropylene (A-1) is high, so that the physical property balance of the molded product is improved.

As a specific method for carrying out the polymerization, a multi-stage polymerization method is typically used. For example, propylene is polymerized to obtain a propylene homopolymer (A-1a) in the first-stage polymerization reactor of a polymerization apparatus equipped with a two-stage polymerization reactor. Block polypropylene (A-1) is obtained by supplying this product to a second-stage polymerization reactor and polymerizing ethylene and propylene, and if necessary, other monomers in this second-stage polymerization reactor. Can be obtained.
The polymerization conditions may be the same as the known polymerization conditions. For example, as the first-stage polymerization condition, a slurry polymerization method in which propylene is in a liquid phase and has high monomer density and productivity can be mentioned. Examples of the second-stage polymerization condition include a vapor phase polymerization method in which a copolymer having high solubility in propylene can be easily produced.
Polymerization (copolymerization of propylene, copolymerization of ethylene, propylene, etc.) is usually carried out using a catalyst. At the time of polymerization, hydrogen may be added to adjust the molecular weight, if necessary.
Prior to the polymerization in the first-stage polymerization reactor, propylene may be prepolymerized in order to form a polymer chain as a foothold for the subsequent main polymerization in the solid catalyst component.

As the catalyst, a known olefin polymerization catalyst can be used.
As the catalyst, a stereospecific Ziegler-Natta catalyst is preferable, and the following catalyst (I) is particularly preferable.
Catalyst (I): A catalyst containing a solid catalyst containing magnesium, titanium, halogen and an electron donor compound, an organoaluminum compound, and an external electron donor compound.

Examples of the electron donor compound (also referred to as “internal electron donor compound”) in the solid catalyst include phthalate compounds, succinate compounds, and diether compounds. A phthalate compound or a succinate compound is preferable because the obtained polypropylene has high stereoregularity and a wide molecular weight distribution. Examples of the phthalate compound include dimethylphthalate, diethylphthalate, dibutylphthalate, diisobutylphthalate, diisopropylphthalate, dioctylphthalate and the like. Examples of the succinate compound include diethyl-2,3- (diisopropyl) succinate, diisobutyl-2,3- (diisopropyl) succinate, di-n-butyl-2,3- (diisopropyl) succinate, diethyl-2,3-. Examples thereof include (dicyclohexyl) -2- (methyl) succinate, diisobutyl-2,3- (dicyclohexyl) -2- (methyl) succinate, and diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid.

Examples of the organic aluminum compound include trialkylaluminum such as triethylaluminum and tributylaluminum, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide, ethylaluminum sesquiethoxydo and butyl. In addition to alkylaluminum sesquialkoxides such as aluminum sesquibutoxide, R ⁷ _2.5 Al (OR ⁸ ) _0.5 (R ⁷ and R ⁸ are hydrocarbon groups that may be different or the same, respectively). Dialkylaluminum halogenides such as partially alkoxylated alkylaluminum, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromid having an average composition represented by. Alkylaluminum sesquihalogenide, ethylaluminum dichloride, propylaluminum dichloride, alkylaluminum dihalogenide, etc. Partially halogenated alkylaluminum, diethylaluminum hydride, dibutylaluminum hydride, etc. Partially hydrided alkylaluminum such as hydride, ethylaluminum dihydride, alkylaluminum dihydride such as propylaluminum dihydride, ethylaluminum ethoxychloride, butylaluminum butokicyclolide, partially alkoxylated such as ethylaluminum ethoxybromid And halogenated alkylaluminum and the like.

External electron donor compounds typically include organosilicon compounds. Preferred organic silicon compounds include, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxy. Silane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, biso-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane , Dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltri Methoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n -Butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxy. Silane, 2-norbornantrimethoxysilane, 2-norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane) ), Vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, methyl (3,3,3-trifluoro-n-propyl) dimethoxysilane, cyclohexylethyldimethoxysilane, cyclopentyl-t-butoxydimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyl Dimethoxysilane, n-propyltrimethoxysilane, di-n-propyldimethoxysilane, texyltrimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butyl-t-butoxydimethoxysilane, isobutyltrimethoxysilane, cyclohexylisobutyldimethoxysilane, di-sec-butyldimethoxysilane, isobutylmethyldimethoxysilane, bis (decahydroisoquinolin-2-yl) Examples thereof include dimethoxysilane, diethylaminotriethoxysilane, dicyclopentyl-bis (ethylamino) silane, tetraethoxysilane, tetramethoxysilane, and isobutyltriethoxysilane.

The method for obtaining blocked polypropylene (A-1) by the multi-stage polymerization method is not limited to the above method, and the propylene homopolymer (A-1a) may be polymerized in a plurality of polymerization reactors, or ethylene. -The propylene copolymer may be polymerized in a plurality of polymerization reactors.
As a method for obtaining the blocked polypropylene (A-1), there is also a method using a polymerizer having a gradient of the monomer concentration and the polymerization conditions. In such a polymerizer, for example, one in which at least two polymerization regions are bonded can be used, and the monomer can be polymerized by vapor phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region consisting of an ascending tube, and a monomer is supplied and polymerized by a descending tube connected to the ascending tube. The polymerization product is recovered while circulating. This method comprises means to prevent the gas mixture present in the ascending tube from entering the descending tube in whole or in part. Further, a gas and / or liquid mixture having a composition different from that of the gas mixture existing in the rising pipe is introduced into the falling pipe. As this polymerization method, for example, the method described in JP-A-2002-520426 can be applied.

The propylene homopolymer (A-2) and the block polypropylene (B) component can also be obtained by the same production method as the block polypropylene (A-1). The electron donor compound in the solid catalyst for synthesizing the component (B) is a succinate-based compound because Mw / Mn of a xylene-insoluble component at 25 ° C., which is in the preferable range described above, can be easily obtained. preferable.

<Effect>
Since the resin composition contains the components (A) to (F) in a specific ratio, it has high fluidity during molding and is suitable for injection molding. Further, the molded product obtained by molding the present resin composition has a low specific density, excellent rigidity, impact resistance, and scratch resistance, and exhibits an appearance of low gloss and suppressed tiger marks.
That is, the tiger mark is suppressed by adding the component (B) to the component (A) which is the base material component, and the impact resistance is improved by adding the component (C) which is an elastomer (). By including (C1) in the C) component, the gloss of the molded product is reduced, and by combining the (D) component, the (E) component and the (F) component, the rigidity and scratch resistance are improved while suppressing the increase in the specific gravity. It will be improved and the balance between rigidity, impact resistance and scratch resistance will be better. Further, since the MFR of the component (A) itself, which is the base material component, is relatively high, the MFR of the entire resin composition can be set high, and high fluidity suitable for injection molding can be obtained. Further, since the component (C1) is contained, the molded product has low gloss even if the content of talc is very small.
Further, when the content of the component (D) is below a certain level and, by extension, the content of talc is below a certain level, the specific gravity of the molded product can be suppressed to a low level, and the weight of the molded product can be reduced.
The fluidity of the present resin composition is sufficiently high for injection molding. For example, even when a thin-walled molded product is obtained by injection molding, molding defects called short shots, in which the resin composition does not spread over a part of the mold cavity, are unlikely to occur. Therefore, this resin composition is useful as a material for injection molding.

〔Molding〕
The molded product of the present invention is a molded product made of the present resin composition.
The molded product of the present invention can be obtained by a known molding method such as injection molding.
The molded product of the present invention can be used, for example, as an automobile interior material, daily necessities, a housing for electric appliances, a food packaging container, and the like. It is particularly suitable as an automobile interior material because it can obtain a molded product having a low specific density, excellent rigidity, impact resistance, and scratch resistance, and having a low gloss and an appearance in which the tiger mark is suppressed.

Examples and comparative examples are shown below, but the present invention is not limited to the following examples.
The measurement methods and materials used in this example are shown below.

〔Measuring method〕
<MFR>
The MFRs of the components (A) and (B) and the MFR of the composition as a whole were measured according to JIS K6921-2 under the conditions of a temperature of 230 ° C. and a load of 2.16 kg.
The MFR of the component (C) was measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K6922-2.
In the case of a mixture in which the component (A) is a block polypropylene (A-1) and a propylene homopolymer (A-2), 0.2 parts by mass of the antioxidant "B225" and the neutralizing agent "DHT" described later will be used. -4A ”0.05 parts by mass is mixed, mixed with a Henshell mixer while stirring for 1 minute, and then a screw rotation speed of 500 rpm is used using a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm. The sample was melt-kneaded under the conditions of a cylinder temperature of 200 ° C. and a discharge rate of 30 kg / hr.

<Density and specific density>
The density of the component (C) is specified in JIS K7112 using a molded product obtained by compression molding at a molding temperature of 180 ° C. and the specific gravity of the composition as a whole using a molded product obtained by injection molding at a molding temperature of 200 ° C. According to the underwater substitution method, the measurement was performed using a hydrometer (ViBRA DMA-220 manufactured by Shinko Denshi Co., Ltd.). The specific gravity of the composition as a whole is preferably 1.0 or less, more preferably 0.99 or less, still more preferably 0.98 or less, from the viewpoint of lightness of the obtained molded product.

<Total ethylene content of polypropylene resin>
For a sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / benzene dehydride, Bruker's AVANCE III HD400 ( ¹³ C resonance frequency 100 MHz) was used, the measurement temperature was 120 ° C, the flip angle was 45 degrees, and the pulse interval was 7. ^{A 13} C-NMR spectrum was obtained under the conditions of seconds, sample rotation speed of 20 Hz, and integration number of 5000 times.
Using the spectrum obtained above, the total ethylene content of the polypropylene resin was determined by the method described in the literature of Kakugo, Y.Naito, K.Mizunuma and T.Miyatake, Macromolecules, 15, 1150-1152 (1982). (Mass%) was calculated.
In the case of a mixture in which the component (A) is a block polypropylene (A-1) and a propylene homopolymer (A-2), 0.2 parts by mass of the antioxidant "B225" and the neutralizing agent "DHT" described later will be used. -4A ”0.05 parts by mass is mixed, mixed with a Henshell mixer while stirring for 1 minute, and then a screw rotation speed of 500 rpm is used using a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm. The sample was melt-kneaded under the conditions of a cylinder temperature of 200 ° C. and a discharge rate of 30 kg / hr.

<Ethylene content of ethylene / propylene copolymer component>
Same as the total ethylene content, except that the integrated strength T'ββ calculated by the following formula was used instead of the integrated strength of Tββ obtained when measuring the total ethylene content of the polypropylene resin by the method described in the above document. The ethylene content (% by mass) in the ethylene / propylene copolymer component (BIPO) was determined by the above method.
T'ββ = 0.98 × Sαγ × A / (1-0.98 × A)
Here, A = Sαγ / (Sαγ + Sαδ), which is calculated from Sαγ and Sαδ described in the above document.

<Content of ethylene / propylene copolymer component in polypropylene resin>
The content (BIPO amount) of the ethylene / propylene copolymer component with respect to the total mass of the polypropylene-based resin was calculated by the following formula.
Content of ethylene / propylene copolymer component (% by mass) = Total ethylene content of polypropylene resin / (Ethylene content in ethylene / propylene copolymer component / 100)

<Ultimate viscosity of xylene-soluble components of polypropylene resin>
The xylene-soluble component of the polypropylene-based resin was obtained by the following method, and the ultimate viscosity (XSIV) of the xylene-soluble component was measured.
2.5 g of a polypropylene resin sample is placed in a flask containing 250 mL of o-xylene (solvent), and the sample is stirred for 30 minutes at 135 ° C. using a hot plate and a reflux device while performing nitrogen purging. After complete dissolution, it was cooled at 25 ° C. for 1 hour. The resulting solution was filtered using filter paper. 100 mL of the filtered filtrate was collected, transferred to an aluminum cup or the like, evaporated to dryness at 140 ° C. while purging with nitrogen, and allowed to stand at room temperature for 30 minutes to obtain a xylene-soluble component.
The ultimate viscosity was measured in tetrahydronaphthalene at 135 ° C. using an automatic capillary viscosity measuring device (SS-780-H1, manufactured by Shibayama Kagaku Kikai Seisakusho Co., Ltd.).

<Mw / Mn of xylene insoluble content of polypropylene resin>
After filtration for obtaining the xylene-soluble component in the above measurement of XSIV, acetone was added to the residue (mixture of xylene-insoluble component and solvent) remaining on the filter paper and filtration was performed. Then, the components remaining on the filter paper without being filtered were evaporated to dryness in a vacuum drying oven set at 80 ° C. to obtain xylene insoluble matter (XI).
Using the above XI as a sample, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are measured as follows, and the mass average molecular weight (Mw) is divided by the number average molecular weight (Mn) to obtain the molecular weight distribution (Mn). Mw / Mn) was calculated.
PL GPC220 manufactured by Polymer Laboratories was used as an apparatus, 1,2,4-trichlorobenzene containing an antioxidant was used as a mobile phase, and UT-G (1) and UT-807 (1) manufactured by Showa Denko KK were used as columns. This) and UT-806M (two) were connected in series, and a differential refractometer was used as a detector. The same solvent as the mobile phase was used as the solvent for the xylene-insoluble sample solution, and the sample was dissolved at a sample concentration of 1 mg / mL for 2 hours while shaking at a temperature of 150 ° C. to prepare a measurement sample. 500 μL of the sample solution thus obtained was injected into the column, and measurements were taken at a flow rate of 1.0 mL / min, a temperature of 145 ° C., and a data acquisition interval of 1 second. A polystyrene standard sample having a molecular weight of 580 to 7.45 million (shodex STANDARD, manufactured by Showa Denko KK) was used for column calibration, and the column was calibrated by a cubic approximation. The coefficients of Mark-Houwink-Sakurada are K = 1.21 × 10 ^-4 , α = 0.707 for polystyrene standard samples, and K = 1.37 × 10 ^-4 , α = for propylene-based polymers. 0.75 was used.

[Manufacturing of polypropylene resin]
<Manufacturing Example 1-1: (A1) -1>
After polymerizing the block polypropylene (A-1) and the propylene homopolymer (A-2) by a known method using a Ziegler-Natta catalyst, a polypropylene-based resin mixture (A1) -1 containing both was obtained. ..
The MFR of the obtained polypropylene-based resin mixture (A1) -1 was 55 g / 10 min.
The mixture (A1) -1 of block polypropylene (A-1) and propylene homopolymer (A-2) is 82% by mass of the total of propylene homopolymer (A-1a) and propylene homopolymer (A-2). And 18% by mass of the ethylene / propylene copolymer (A-1b), and the ultimate viscosity (XSIV) of the xylene-soluble component of the block polypropylene (A-1) at 25 ° C. is 2.1 dL / g. The ethylene unit in the ethylene / propylene copolymer (A-1b) was 37% by mass.
The MFR of the propylene homopolymer (A-2) used here was 1800 g / 10 min. The content of the propylene homopolymer (A-2) is 8% by mass when the total mass of the (A) component, the (B) component, the (C) component, and the (D) component is 100% by mass. there were.

<Manufacturing Example 1-2: (A1) -2>
After polymerizing block polypropylene (A-1) different from Production Example 1-1 by the same method as in Production Example 1-1, a propylene homopolymer having the same MFR as Production Example 1-1 at 1800 g / 10 min ( A mixture (A1) -2 of a polypropylene-based resin containing A-2) was obtained.
The MFR of the obtained polypropylene-based resin mixture (A1) -2 was 55 g / 10 min.
The mixture (A1) -2 of block polypropylene (A-1) and propylene homopolymer (A-2) is a total of 82% by mass of the propylene homopolymer (A-1a) and the propylene homopolymer (A-2). And 18% by mass of the ethylene / propylene copolymer (A-1b), and the ultimate viscosity (XSIV) of the xylene-soluble component of the block polypropylene (A-1) at 25 ° C. is 2.4 dL / g. The ethylene unit in the ethylene / propylene copolymer (A-1b) was 30% by mass.
The content of the propylene homopolymer (A-2) is 5% by mass when the total mass of the (A) component, the (B) component, the (C) component, and the (D) component is 100% by mass. there were.

<Manufacturing Example 1-3: (A1) -3>
After polymerizing block polypropylene (A-1) different from Production Example 1-1 and Production Example 1-2 by the same method as Production Example 1-1, the same MFR as Production Example 1-1 is 1800 g / 10 min. A polypropylene-based resin mixture (A1) -3 containing a certain propylene homopolymer (A-2) was obtained.
The MFR of the obtained polypropylene-based resin mixture (A1) -3 was 55 g / 10 min.
The mixture (A1) -3 of block polypropylene (A-1) and propylene homopolymer (A-2) is a total of 82% by mass of the propylene homopolymer (A-1a) and the propylene homopolymer (A-2). And 18% by mass of the ethylene / propylene copolymer (A-1b), and the ultimate viscosity (XSIV) of the xylene-soluble component of the block polypropylene (A-1) at 25 ° C. is 2.1 dL / g. The ethylene unit in the ethylene / propylene copolymer (A-1b) was 26% by mass.
The content of the propylene homopolymer (A-2) is 5% by mass when the total mass of the (A) component, the (B) component, the (C) component, and the (D) component is 100% by mass. there were.

<Manufacturing example 2: (A2)>
A polypropylene-based resin containing the same block polypropylene (A-1) as in Production Example 1-1 and a propylene homopolymer (A-2) different from Production Example 1-1 polymerized by the same method as Production Example 1-1. (A2) was obtained.
The MFR of the obtained polypropylene-based resin mixture (A2) was 80 g / 10 min.
The mixture (A2) of block polypropylene (A-1) and propylene homopolymer (A-2) is a total of 82% by mass of propylene homopolymer (A-1a) and propylene homopolymer (A-2) and ethylene. -It consisted of 18% by mass of the propylene copolymer (A-1b).
The MFR of the propylene homopolymer (A-2) used here exceeded 2000 g / 10 min, which was too high to measure. The content of the propylene homopolymer (A-2) is 12% by mass when the total mass of the (A) component, the (B) component, the (C) component, and the (D) component is 100% by mass. there were.

〔material〕
(A) Component (A1) -1: Polypropylene resin produced in Production Example 1-1.
(A1) -2: Polypropylene resin produced in Production Example 1-2.
(A1) -3: Polypropylene resin produced in Production Example 1-3.
(A2): Polypropylene resin produced in Production Example 2. MFR is relatively high as compared with (A1) -1 to (A1) -3.

Component (B1): The weight ratio of TEAL to the solid catalyst of the solid catalyst component prepared based on the examples of JP2011-500907 and triethylaluminum (TEAL) and dicyclopentyldimethoxysilane (DCPMS) The contact was carried out at room temperature for 5 minutes in an amount such that the weight ratio of TEAL / DCPMS was 18. Prepolymerization was carried out by holding the obtained catalyst system in a suspended state in liquid propylene at 20 ° C. for 5 minutes.
The obtained prepolymer was introduced into the first-stage polymerization reactor to obtain a propylene homopolymer (B-1a), and then the obtained polymer was purged of unreacted monomers and then two-stage. It was introduced into an eye polymerization reactor to polymerize an ethylene-propylene copolymer (B-1b). During the polymerization, the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier. The amount of the ethylene / propylene copolymer (B-1b) component was adjusted according to the residence time distributions of the first and second stages.
0.2 parts by mass of the antioxidant "B225" and 0.05 parts by mass of the neutralizing agent "DHT-4A", which will be described later, are mixed with the powder of the block polypropylene polymer produced in this manner, and 1 by mass using a Henschel mixer. After stirring and mixing for 1 minute, the mixture was melt-kneaded and extruded at a cylinder temperature of 200 ° C. using a single-screw extruder (manufactured by Nakatani Machinery Co., Ltd., model number NVC-50) having a screw diameter of 50 mm. After cooling the strands in water, they were cut with a pelletizer to obtain pellets.
The obtained (B1) is a block polypropylene composed of 70% by mass of the propylene homopolymer (B-1a) and 30% by mass of the ethylene / propylene copolymer (B-1b), and has a molecular weight distribution of xylene insoluble matter (Mw). / Mn) is 10, the ultimate viscosity (XSIV) of the xylene-soluble component at 25 ° C. is 7.0 dL / g, and the MFR is 9.5 g / 10 min, which is a polypropylene resin. The ethylene unit in the ethylene / propylene copolymer (B-1b) is 30% by mass.

(C) Ingredient (C1): "Engage HM7487" manufactured by Dow Chemical Co., Ltd. An elastomer composed of an ethylene-1-butene copolymer having 4 carbon atoms, a long-chain branch, an MFR of 0.6 g / 10 min, and a density of 0.860 g / cm ^3. ..
(C2): "Toughmer A-1050S" manufactured by Mitsui Chemicals, Inc. An elastomer composed of an ethylene-1-butene copolymer having no long chain branching, an MFR of 1.2 g / 10 min, and a density of 0.860 g / cm ^3. It is an elastomer for comparison.
(C3): "Toughmer A-0550S" manufactured by Mitsui Chemicals, Inc. An elastomer composed of an ethylene-1-butene copolymer having no long chain branch, an MFR of 0.9 g / 10 min, and a density of 0.861 g / cm ^3. It is an elastomer for comparison.

(D) Ingredient: Talc "Neo Talc UNI05" manufactured by Neolite Kosan Co., Ltd.
(E) Ingredient: "ADEKA STAB NA18" manufactured by ADEKA CORPORATION. 2,4,8,10-Tetra (tert-butyl) -6-hydroxy-12H-dibenzo [d, g] [1,3,2] Phosphate ester-based sodium salt containing dioxaphosphocin 6-oxide sodium salt It is a crystal nucleating agent.
(F) Ingredient: Erucic acid amide "Alflow P-10" manufactured by NOF CORPORATION. It is a higher fatty acid amide.

Other Ingredients Antioxidant: "B225" manufactured by BASF.
Neutralizer: "DHT-4A" manufactured by Kyowa Chemical Industry Co., Ltd.
Weatherproofing agent: "ADEKA STAB LA502XP" manufactured by ADEKA CORPORATION.
Lubricants: "Magnesium stearate" manufactured by NOF CORPORATION.

<Example 1>
66% by mass of the polypropylene-based resin (A1) -1 obtained in Production Example 1-1, 10% by mass of the block polypropylene of (B1), and 11% by mass of "Engage HM7487" of (C1). With 13% by mass of the component (D) "Neotalc UNI05" and 100 parts by mass of these total masses, 0.15 parts by mass of the component "Adecastab NA-18" and the above (F). 0.3 parts by mass of the component "Alflow P-10", 0.2 parts by mass of the antioxidant "B225", and 0.05 parts by mass of the neutralizer "DHT-4A". 0.4 parts by mass of the weather resistant agent "Adecastab LA502XP" and 0.1 parts by mass of the lubricant "magnesium steerate" were mixed and mixed with a Henshell mixer for 1 minute, and then the screw diameter was 30 mm. The two-screw extruder (TEX30α manufactured by Nippon Steel Co., Ltd.) was used for melt-kneading under the conditions of a screw rotation speed of 500 rpm, a cylinder temperature of 200 ° C., and a discharge rate of 30 kg / hr. The extruded strands were cooled in water and then cut with a pelletizer to obtain pellets of a polypropylene resin composition having the composition shown in Table 1.

<Examples 2 to 5, Comparative Examples 1 to 8>
Pellets of a polypropylene-based resin composition were obtained in the same manner as in Example 1 except that the type and amount of the materials to be mixed were changed so as to have the compositions shown in Table 1. In each example, although not shown in Table 1, the antioxidant "B225", the neutralizer "DHT-4A", the weathering agent "Adecastab LA502XP", and the lubricant "magnesium steer". "Rate" was blended in the same proportion as in Example 1.

For the polypropylene-based resin composition obtained in each example, MFR, which is an index of fluidity, was measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K6921-2. Further, for the polypropylene resin composition of each example, the flexural modulus which is an index of rigidity, the Charpy impact strength which is an index of impact resistance, the mirror glossiness, the distance to the tiger mark, and the scratch resistance are applied by the following methods. Gender was evaluated. These results are also shown in Table 1.

(Flexural modulus)
According to JIS K6921-2, using an injection molding machine (FANUC ROBOSHOT S2000i manufactured by FANUC Co., Ltd.), the molten resin temperature is 200 ° C., the mold temperature is 40 ° C., the average injection speed is 200 mm / sec, the holding time is 40 seconds, and the total cycle time is 60. Under the condition of seconds, a multipurpose test piece (type A1) specified in JIS K7139 is injection-molded using a polypropylene-based resin composition as a raw material, processed into a width of 10 mm, a thickness of 4 mm, and a length of 80 mm, and a measurement test is performed. Pieces (type B2) were obtained. Using a precision universal testing machine (Autograph AG-X 10kN) manufactured by Shimadzu Corporation, a test piece for type B2 measurement under the conditions of temperature 23 ° C, relative humidity 50%, distance between fulcrums 64 mm, and test speed 2 mm / min. The flexural modulus was measured. From the viewpoint of the rigidity of the molded product, the flexural modulus is preferably 1750 MPa or more, more preferably 1800 MPa or more.

(Charpy impact strength)
Using a type A1 test piece obtained by the same operation as the test piece used for flexural modulus measurement, according to JIS K7111-1, using a notching tool A-4 manufactured by Toyo Seiki Seisakusho Co., Ltd., width 10 mm, thickness 4 mm, After processing to a length of 80 mm, a notch of 2 mm was made in the width direction to obtain a test piece for measurement of shape A. For the test piece for measurement, a fully automatic impact tester with a low temperature tank (No. 258-ZA) manufactured by Yasuda Seiki Seisakusho Co., Ltd. was used, and the Charpy impact strength (edgewise impact, 1eA method) was applied under the condition of a temperature of -20 ° C. It was measured. From the viewpoint of impact resistance of the molded article, the Charpy impact strength is preferably 4.0 kJ / ^{m 2} or more, 4.5kJ / ^{m 2} or more is more preferable.

(Mirror gloss)
The test flat plate was manufactured using an EC160NII injection molding machine manufactured by Toshiba Machine Co., Ltd. under molding conditions of a cylinder temperature of 210 ° C., a mold temperature of 40 ° C., an injection time of 15 seconds, and a cooling time of 25 seconds. As a mold corresponding to the size of the test flat plate, a mirror-faced mold having a film gate and equipped with a nest of 300 (length) × 140 (width) × 3 mm (thickness) was used. With respect to the obtained test flat plate, the mirror glossiness (%) at an incident angle of 60 ° was measured using a gloss meter (GM-26PRO) manufactured by Murakami Color Research Institute Co., Ltd. according to JIS Z8741. The lower the value, the lower the gloss, and the higher the appearance and the better. From such a viewpoint, the mirror glossiness is preferably 65% or less, more preferably 60% or less, still more preferably 55% or less.

(Distance to Tiger Mark)
The appearance of the test flat plate used for the evaluation of the mirror glossiness was visually observed, and the distance (mm) from the gate position to the position where the tiger mark started to occur was measured. The longer the distance, the better the appearance of the molded product. From such a viewpoint, the distance to the tiger mark is preferably 170 mm or more, more preferably 180 mm or more, and even more preferably 190 mm or more.

(Scratch resistance)
Using the test plate used for the mirror gloss evaluation, a surface quality measuring machine (HEIDON-14D manufactured by Shinto Kagaku Co., Ltd.) equipped with a tungsten steel needle (R = 0.1 mm) was used at a temperature of 23 ° C. and a load of 0. Under the condition of 5N, 20 scratches having a length of 50 mm were formed at a speed of 550 mm / min at 1 mm intervals in a direction orthogonal to the flow direction at the time of injection molding. ^{The brightness difference ΔL *} between the scratched portion and the normal portion of the test plate was measured by a spectrocolorimeter (SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS Z8730. ΔL ^* is an index of scratch resistance, and the smaller this value is, the better the scratch resistance is. From such a viewpoint, ΔL ^* is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.

In Table 1, the contents of the component (A), the component (B), the component (C) and the component (D) are ratios (mass%) to the total mass (100% by mass) of these. The contents of the components (E), (F) and other components other than these are the ratio (parts by mass) of the components (A), (B), (C) and (D) to 100 parts by mass in total. ).
In the column of the component (C) in Table 1, for example, "(C1), (C2)" means that (C1) and (C2) are contained, and the content thereof is also the same.

The polypropylene-based resin compositions of Examples 1 to 5 had a high MFR and were suitable for injection molding. The molded article of each example had an excellent balance of physical properties of rigidity and impact resistance, low gloss, low specific gravity, suppressed tiger mark, and good scratch resistance.
In the composition of Comparative Example 1, the MFR of the block polypropylene (A-1) as a component (A) was high, and the MFR of the entire composition was also high. Therefore, the impact resistance was inferior.
The composition of Comparative Example 2 did not contain the component (B), was inferior in impact resistance, and had a conspicuous tiger mark.
In the composition of Comparative Example 3, the component (C) was an elastomer having no long-chain branching, and the surface was shining due to its high gloss, and the tiger mark was conspicuous.
In the composition of Comparative Example 4, the content of the component (C1) was low and the gloss was high, so that the surface looked shiny and the tiger mark was conspicuous.
The composition of Comparative Example 5 had a low content of the component (D) and was inferior in rigidity.
The composition of Comparative Example 6 had a large content of the component (D), a large specific density, and was inferior in lightness.
The composition of Comparative Example 7 had a small content of the component (E) and was inferior in rigidity.
The composition of Comparative Example 8 had a small content of the component (F) and was inferior in scratch resistance.

Claims (4)

A polypropylene resin as a component (A), a polypropylene resin as a component (B), an ethylene / α-olefin copolymer as a component (C), a filler as a component (D), and a component (E). Contains a crystal nucleating agent and a higher fatty acid amide which is a component (F).
The component (A) is a block polypropylene (A-1) composed of a propylene homopolymer (A-1a) and an ethylene / propylene copolymer (A-1b), and if necessary, according to JIS K6921-2. The polypropylene homopolymer (A-2) having an MFR of 500 to 2000 g / 10 min measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg further contains a propylene homopolymer (A-1a) and a propylene homopolymer (A). According to JIS K6921-2, which comprises 75 to 90% by mass of the total propylene homopolymer including -2) and 10 to 25% by mass of the ethylene / propylene copolymer (A-1b), the temperature is 230 ° C. and the load is 2. It is a polypropylene resin (A1) having an MFR of 40 to 70 g / 10 min measured under the condition of 16 kg.
The ultimate viscosity (XSIV) of the xylene-soluble component of the block polypropylene (A-1) at 25 ° C. is 0.5 to 4.0 dL / g, and is contained in the ethylene-propylene copolymer (A-1b). The ethylene unit content is 20 to 50% by mass,
The component (B) is composed of 60 to 80% by mass of the propylene homopolymer (B-1a) and 20 to 40% by mass of the ethylene / propylene copolymer (B-1b), and has a temperature of 230 according to JIS K6921-2. The MFR measured under the conditions of ° C. and a load of 2.16 kg was 5 to 30 g / 10 min, the Mw / Mn of the xylene insoluble component at 25 ° C. was 6 to 20, and the extreme viscosity of the xylene soluble component at 25 ° C. (XSIV) is a polypropylene-based resin made of block polypropylene having a value of 5.5 to 9.0 dL / g.
The ethylene unit content in the ethylene / propylene copolymer (B-1b) is 20 to 40% by mass.
The component (C) has an α-olefin having 4 to 8 carbon atoms, has a long-chain branch, and has an MFR of 0. It contains the component (C1), which is an elastomer composed of an ethylene / α-olefin copolymer having a density of 1 to 5 g / 10 min and a density of 0.857 to 0.873 g / cm ^3.
When the total mass of the component (A), the component (B), the component (C), and the component (D) is 100% by mass, the content of the component (A) is 45 to 81% by mass. The content of the component (B) is 4 to 20% by mass, the content of the component (C1) is 5 to 20% by mass, and the content of the component (D) is 10% by mass or more. Less than 15% by weight
When the total mass of the component (A), the component (B), the component (C), and the component (D) is 100 parts by mass, the content of the component (E) is 0.05 to 0. .. A polypropylene resin composition having 4 parts by mass and a content of the component (F) of 0.05 to 0.5 parts by mass. The polypropylene-based resin composition according to claim 1, wherein the MFR of the entire composition is 20 to 35 g / 10 min, measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg according to JIS K6921-2. When the total mass of the component (A), the component (B), the component (C), and the component (D) is 100% by mass, the content of the propylene homopolymer (A-2) is The polypropylene-based resin composition according to claim 1 or 2, which is 2 to 20% by mass. A molded product obtained from the polypropylene-based resin composition according to any one of claims 1 to 3.