JP2009019119A - Polypropylene resin composition and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene resin composition having excellent impact resistance and transparency and capable of forming a molding with increased crystallization rate, reduced molding cycle and improved productivity. <P>SOLUTION: The polypropylene resin composition is obtained by blending 0.05-2 pts.wt. specific dibenzylidene sorbitols (D), 0.001-0.5 pts.wt. specific metal salt (E) such as a metal salt of hexahydrophthalic acid group and 0-1 pts.wt. specific aliphatic organic acid metal salt (F) with 100 pts.wt. resin mixture containing 50-91 wt.% specific propylene-ethylene random copolymer (component (A)), 7-30 wt.% propylene monopolymer (component (B)) and 2-20 wt.% specific ethylene based copolymer (component (C)). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polypropylene resin composition and a molded body comprising the same. More specifically, a polypropylene resin composition that is excellent in surface impact and transparency, and has a high crystallization speed, shortens the molding cycle and improves productivity when formed into a molded body, and a molded body comprising the same. It is about.

A polypropylene resin composition has been conventionally used for food containers and the like because it can be made into a thin and transparent injection-molded product. As a polypropylene-based resin composition used for such applications, for example, ethylene polymerized in Japanese Patent Application Laid-Open No. 2004-176061 (Patent Document 1) using a specific propylene / ethylene random copolymer and a specific metallocene catalyst. A polypropylene resin composition is described in which an organic peroxide is added to a mixture containing an α-olefin copolymer and a specific propylene homopolymer and melt kneaded.
Japanese Patent Application Laid-Open No. 10-77373 (Patent Document 2) describes a specific polypropylene resin and a refractive index of a polypropylene resin for the purpose of improving transparency while maintaining a good balance between rigidity and impact resistance. A polypropylene-based resin composition is described in which an ethylene / α-olefin copolymer having a difference in a specific range is blended at a specific ratio.
JP-A-10-45970 (Patent Document 3) discloses a polypropylene-based resin having a specific refractive index and a polyolefin-based rubber for the purpose of improving impact resistance while maintaining excellent transparency. A polypropylene-based resin composition containing a specific transparent nucleating agent is described.
JP-A-9-20840 (Patent Document 4) discloses a specific polypropylene-based resin, a specific ethylene-based copolymer and a specific polypropylene-based resin for the purpose of improving the balance of gloss, heat resistance, rigidity, and impact resistance. And a polypropylene resin composition containing a sorbitol nucleating agent.
Japanese Patent Application Laid-Open No. 9-32164 (Patent Document 5) discloses that a specific ethylene (co) weight is added to a propylene-based polymer for the purpose of improving transparency and impact resistance while keeping few heat resistance and elution components. A polypropylene resin composition characterized by comprising a coalesced polymer and another ethylene polymer is described.
JP 2004-176061 A Japanese Patent Laid-Open No. 10-77373 Japanese Patent Laid-Open No. 10-45970 Japanese Patent Laid-Open No. 9-20840 Japanese Patent Laid-Open No. 9-32164

However, the polypropylene resin composition described in the above publication is also excellent in impact resistance and transparency. Further, when formed into a molded body, the crystallization speed is fast and the molding cycle can be shortened, and the productivity It was desired to improve.
Under such circumstances, an object of the present invention is a polypropylene resin that is excellent in impact resistance and transparency, and that when formed into a molded body, the crystallization speed is high, the molding cycle can be shortened, and the productivity can be improved. The object is to provide a composition and an injection-molded body comprising the same.

As a result of intensive studies, the present inventors have found that the present invention can solve the above problems, and have completed the present invention.
That is, the present invention
The following propylene-ethylene random copolymer (component (A)) 50 to 91 wt%, the following propylene homopolymer (component (B)) 7 to 30 wt%, the following ethylene copolymer (component (C)) 2 to 20% by weight of the resin mixture (the total of component (A), component (B) and component (C) is 100% by weight), and 100 parts by weight of the resin mixture,
The following general formula (I)

(In formula (I), R ^{1 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms). At least one dibenzylidene sorbitol (D) of 0.05 to 2 parts by weight;
The following general formula (II)

(In the formula (II), M ₁ and M ₂ are each selected from the group consisting of a sodium atom and a hydrogen atom, wherein at least one of M ₁ and M ₂ is a sodium atom, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each hydrogen, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, or 1 to 9 carbon atoms. Alkoxy group, alkyleneoxy group having 1 to 9 carbon atoms, amino group, alkylamine group having 1 to 9 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), and phenyl group Wherein, when these groups are alkyl groups, the alkyl groups may combine to form a carbocyclic ring having up to 6 carbon atoms, the compound having a trans or cis configuration Either At least one metal salt (E) represented by cis configuration, and 0.001 to 0.5 parts by weight,
The following general formula (III)

(In the formula (III), R ²¹ represents a group introduced from an aliphatic organic acid having 10 to 30 carbon atoms, M ³ represents an alkali metal atom, an alkaline earth metal atom or a zinc atom, and n represents 1 or 2 is represented.) At least one aliphatic organic acid metal salt (E) represented by 0 to 1 part by weight is included in the polypropylene resin composition.
Ingredient (A):
The content of structural units derived from ethylene is 2 to 5% by weight,
Propylene-ethylene random copolymer having a melt flow rate (JIS-K6758) measured at a measurement temperature of 230 ° C. and a load of 2.16 kgf of 2 to 90 g / 10 minutes (however, the total amount of propylene-ethylene random copolymer is 100 %).
Ingredient (B):
A propylene homopolymer having a melt flow rate (JIS-K6758) measured at a measurement temperature of 230 ° C. and a load of 2.16 kgf of 2 to 150 g / 10 minutes.
Component (C):
Propylene having a density of 0.86 to 0.91 g / cm ³ , a melt flow rate (JIS-K7210) measured at a measurement temperature of 190 ° C. and a load of 2.16 kgf of 2 to 100 g / 10 min, and a carbon number of 4 A copolymer obtained by copolymerizing at least one olefin selected from -18 α-olefins and ethylene.

  According to the present invention, a polypropylene resin composition having excellent surface impact properties and transparency, and, when formed into a molded body, has a high crystallization speed and can shorten a molding cycle and improve productivity, and a molding comprising the same. You can get a body.

The propylene-ethylene random copolymer (component (A)) used in the present invention is a propylene-ethylene random copolymer having a content of structural units derived from ethylene of 2 to 5% by weight (provided that propylene-ethylene is used). The total amount of random copolymer is 100% by weight). The content of the structural unit derived from ethylene is preferably 2 to 4% by weight.
When the content of the structural unit derived from ethylene is less than 2% by weight, the surface impact property may be insufficient, and when it exceeds 5% by weight, the crystallization speed and rigidity may be insufficient.
The melt flow rate (hereinafter referred to as MFR) (JIS-K6758) measured at a measurement temperature of 230 ° C. and a load of 2.16 kgf of component (A) is 2 to 90 g / 10 minutes, preferably 10 to 90 g / 10 minutes. More preferably, it is 20-50 g / 10min. When the MFR of the component (A) is less than 2 g / 10 minutes, the moldability may be insufficient, and when it exceeds 90 g / 10 minutes, the impact strength and surface impact may be insufficient.
The content of the component (A) contained in the polypropylene resin mixture of the present invention is 50 to 91% by weight (the sum of the component (A), the component (B) and the component (C) is 100% by weight), Preferably it is 70 to 91% by weight. When the content of the component (A) is less than 50% by weight, sufficient transparency and surface impact may not be obtained. When it exceeds 91% by weight, a sufficient crystallization speed cannot be obtained and molding is performed. Cycle performance may not be shortened sufficiently.

The melt flow rate (hereinafter referred to as MFR) (JIS-K6758) measured at a measurement temperature of 230 ° C. and a load of 2.16 kgf of the propylene homopolymer (component (B)) used in the present invention is 2 to 150 g / 10 min. And preferably 15 to 70 g / 10 min. When the MFR of the component (C) is less than 0.5 g / 10 minutes, the moldability may be insufficient, and when it exceeds 150 g / 10 minutes, the surface impact may be insufficient.
The isotactic pentad fraction measured by ¹³ C-NMR of component (B) is preferably 0.95 or more from the viewpoint of increasing rigidity, heat resistance or crystallization time, and more preferably, 0.97 or more.
The isotactic pentad fraction is defined as the method published by A. Zambelli et al., Macromolecules, 6,925 (1973), i.e., the isoform of pentad units in a polypropylene molecular chain measured using ¹³ C-NMR. The fraction of units derived from propylene monomer at the center of a tactic chain, in other words, a chain of five meso-bonded propylene monomer units in succession (however, the assignment of the NMR absorption peak is the Macromolecules, 8,687 (1975)). Specifically, the isotactic pentad fraction is measured as the area fraction of the mmmm peak in the total absorption peak in the methyl carbon region of the ¹³ C-NMR spectrum. The isotactic pentad fraction of NPL standard substance CRM No. M19-14 Polypropylene PP / MWD / 2 of NATIONAL PHYSICAL LABORATORY, UK was measured by this method and found to be 0.944.
The molecular weight distribution (Q value, Mw / Mn) measured by gel permeation chromatography (GPC) of the component (B) is preferably 3 or more and 7 or less, more preferably 3-5.
The content of component (B) is 7 to 30% by weight (the total of component (A), component (B) and component (C) is 100% by weight), preferably 10 to 20% by weight. is there. When the content of the component (B) is less than 7% by weight, a sufficient crystallization rate may not be obtained, and when it exceeds 30% by weight, sufficient transparency and impact resistance may not be obtained. is there.

The polyethylene-based copolymer (component (C)) used in the present invention is a copolymer obtained by copolymerizing at least one olefin selected from propylene and an α-olefin having 4 to 18 carbon atoms with ethylene. It is.
Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethyl- Examples include pentene-1. These may be used alone or in combination of at least two kinds.
The density of the component (C), from the viewpoint of transparency and surface impact resistant, 0.86~0.91g / cm ^3, preferably 0.88~0.91g / cm ^3. When the density is 0.86 g / cm ³ or less, transparency may be insufficient, and when it exceeds 0.91 g / cm ³ , transparency and surface impact may be insufficient.
The melt flow rate (hereinafter referred to as MFR) (JIS-K7210) measured at a measurement temperature of 190 ° C. and a load of 2.16 kgf of component (C) is 2 to 100 g / 10 minutes, preferably 5 to 50 g / 10 minutes. It is. When the MFR of the component (B) is less than 2 g / 10 minutes, transparency and formability may be insufficient, and when it exceeds 100 g / 10 minutes, surface impact may be insufficient.
The content of (C) is 2 to 20% by weight (the total of component (A), component (B) and component (C) is 100% by weight), preferably 4 to 10% by weight. . When the content of the component (C) is less than 2% by weight, sufficient impact resistance may not be obtained. When the content exceeds 20% by weight, a sufficient crystallization rate cannot be obtained, and the molding cycle property is low. It may not be shortened sufficiently.

  The dibenzylidene sorbitols (D) used in the present invention are represented by the following general formula (I)

(In formula (I), R ^{1 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms). At least one dibenzylidene sorbitol.
Here, as a halogen atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably it is a chlorine atom. Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above, preferably a methyl group and an ethyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include an alkoxy group in which the alkyl portion is the same alkyl as the alkyl having 1 to 4 carbon atoms contained in the alkyl having 1 to 8 carbon atoms. Preferably, it is a methoxy group or an ethoxy group.
Examples of the dibenzylidene sorbitols (D) used in the present invention include 1,3: 2,4-di (p-methylbenzylidene) sorbitol, 1,3-o-methylbenzylidene 2,4-p-methylbenzylidene. Sorbitol, 1,3: 2,4-dibenzylidene sorbitol, 1,3: 2,4-di- (p-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol From the viewpoint of odor, 1,3,4,4-di (benzylidene) sorbitol is preferable.
The compounding amount of the dibenzylidene sorbitols (D) used in the present invention is 0.05 to 2 parts by weight with respect to 100 parts by weight of the resin mixture (component (A), component (B) and component (C)). Preferably 0.1 to 1 part by weight, more preferably 0.15 to 0.5 part by weight. If the amount of dibenzylidene sorbitol (C) is less than 0.05 parts by weight, the effect of improving the transparency, mechanical strength and moldability is insufficient, and if it exceeds 2 parts by weight, the resin Dispersibility with respect to the components (component (A), component (B) and component (C)) may deteriorate and mechanical properties such as impact resistance may deteriorate, and the effect of improving transparency will be saturated. It will only be uneconomical.
The dibenzylidene sorbitols (D) are preferably used as a powder. The powder characteristics of the dibenzylidene sorbitols (D) are preferably such that the apparent bulk specific gravity is in the range of 0.1 to 0.5 g / cc, more preferably 0.2 to 0.4 g / cc. The apparent bulk specific gravity is the weight of the dibenzylidene sorbitol (D) powder when the dibenzylidene sorbitol (D) powder is stacked in a constant volume by a natural drop and deposited in a certain volume. Is obtained by calculation. If it is smaller than the above range, there may be no fluidity at the time of blending and the productivity may deteriorate, and if it is larger, the dispersibility with respect to the resin components (component (A), component (B) and component (C)) The mechanical properties such as impact resistance may be deteriorated due to deterioration, the effect of improving the transparency may not be sufficient, or white spots may be confirmed on the molded product, resulting in poor appearance.
As a manufacturing method of dibenzylidene sorbitol (D), a well-known manufacturing method is mentioned. Examples of a method for producing a powder of dibenzylidene sorbitol (D) include a pulverization method and a method of production by changing the precipitation conditions during the particle production process, and in order to prevent aggregation of particles during production. Alternatively, it may be produced in a state in which a surface treatment agent, a surfactant or the like is brought into contact.
The metal salts (E) used in the present invention are represented by the following general formula (II)

(In the formula (II), M ₁ and M ₂ are selected from the group each consisting of sodium and hydrogen atoms, at least one of wherein M ₁ and M ₂ is sodium atom, R ^11, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each hydrogen, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, or 1 to 9 carbon atoms. Alkoxy group, alkyleneoxy group having 1 to 9 carbon atoms, amino group, alkylamine group having 1 to 9 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), and phenyl group Wherein, when these groups are alkyl groups, the alkyl groups may combine to form a carbocyclic ring having up to 6 carbon atoms, the compound having a trans or cis configuration Either And preferably a cis configuration.).
Examples of the metal salts represented by the general formula (II) include compounds described in JP-T-2004-524417 and JP-A-2004-530006.
The metal salt (E) represented by the general formula (II) is more preferably a metal salt of a hexahydrophthalic acid group, more preferably disodium-bicyclo (2, represented by the following structural formula: 2,1) Heptane-2,3-dicarboxylate.
The content of the metal salt (E) used in the present invention is 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the resin mixture (component (A), component (B) and component (C)). Preferably, it is 0.005-0.04 weight part, More preferably, it is 0.01-0.03 weight part. When the amount is less than 0.001 part by weight, the improvement of transparency and crystallization speed may be insufficient. When the amount exceeds 0.04 part by weight, the effect of improving the transparency and surface impact may not be sufficient. And it's just overkill and uneconomical.
In addition, the blending ratio of the component (D) and the component (E) used in the present invention is preferably in the range of (D) / (E) of 3 to 300 from the viewpoints of transparency, molding processability, and mechanical properties. More preferably, (D) / (E) is in the range of 5 to 100, particularly preferably in the range of 5 to 50. This blending ratio can be arbitrarily selected as long as the object of the present invention is not impaired.
In addition, the aliphatic organic acid metal salts (F) used in the present invention have the general formula (III)

(In the formula (III), R ²¹ represents a group introduced from an aliphatic organic acid having 10 to 30 carbon atoms, M ³ represents an alkali metal atom, an alkaline earth metal atom or a zinc atom, and n represents Represents at least one aliphatic organic acid metal subsalt represented by 1 or 2.
In the aliphatic organic acid metal salt (III), the R ²¹ group is a group derived from an aliphatic organic acid having 10 to 30 carbon atoms, and the organic acid may have a hydroxyl group, such as capric acid, neodecane. Acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, succinic acid, Linderic acid, Tuzuic acid, Palmitoleic acid, Petrothelic acid, Oleic acid, Elaidic acid, Vaccenoic acid, Linoleic acid, Linoleic acid, Gamma-linolenic acid, Linolenic acid, Ricinoleic acid, 12-Hydroxystearic acid, Naphthenic acid, Abietin An acid etc. are mentioned. Of these, stearic acid and 12-hydroxystearic acid are preferable because of low cost and remarkable use effects. Examples of the alkali metal represented by M ³ include lithium, sodium, and potassium, and examples of the alkaline earth metal include magnesium, calcium, strontium, and barium.
Among them, the viewpoint of improving the dispersibility of the dibenzylidene sorbitols (D) and the metal salts (E) represented by the general formula (II) with respect to the resin components (component (A), component (B) and component (C)) From the above, lithium and sodium which are alkali metals are preferable.
The aliphatic organic acid metal salt (F) is used in an amount of 0 to 1 part by weight based on 100 parts by weight of the resin mixture (component (A), component (B) and component (C)) used in the present invention. It is arbitrarily selected and blended within the range. When blended, from the viewpoint of further improving the transparency, mechanical properties, and moldability, it is preferably in the range of 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.01 parts by weight. Range.

The melt flow rate (MFR) of the polypropylene resin composition of the present invention is preferably 10 to 100 g / 10 minutes, more preferably 20 to 50 g / 10, from the viewpoint of improving moldability, ductility and impact resistance. Minutes. The melt flow rate (MFR) of the polypropylene resin composition is a melt flow rate (JIS-K6758) measured at a measurement temperature of 230 ° C. and a load of 2.16 kgf.
In the production of the polypropylene resin composition of the present invention, as a method of adjusting the melt flow rate (MFR) measured at 230 ° C. to the range of 10 to 100 g / 10 minutes, a propylene-ethylene random copolymer (component (A)) ), A propylene homopolymer (component (B)), an ethylene copolymer (component (C)), a component (D), a component (E), and (F) as necessary. It can be adjusted by modification by melt mixing in the presence of the oxide (G).

The organic peroxide (G) used in the present invention is alkyl peroxides, diacyl peroxides, peroxide esters and peroxide carbonates.
Examples of alkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, di-t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butylcumyl, 1,3-bis (t-butylperoxyisopropyl) benzene, 3,6,9-triethyl- 3,6,9-trimethyl-1,4,7-triperoxonane and the like can be mentioned.
Examples of the diacyl peroxides include benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, and the like.
Examples of the peroxide esters include 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, and t-butyl. Peroxyneoheptanoate, t-butylperoxypivalate, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxyl- 2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy3,5,5 -Trimethylhexanoate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxy Oxyacetate, t- butyl peroxybenzoate, di - butylperoxy trimethyl Adi adipate, and the like.
Examples of the peroxide carbonates include di-3-methoxybutyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, diisopropyl peroxycarbonate, t-butylperoxyisopropyl carbonate, and di (4-t- Butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate and the like.
As the organic peroxide (G), alkyl peroxides are preferable, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butyl) is particularly preferable. Peroxyisopropyl) benzene, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan.
The compounding quantity of an organic peroxide (G) is 0-0.5 weight part with respect to 100 weight part of said resin mixtures (component (A), component (B), and component (C)). Preferably it is 0.0005-0.3 weight part, More preferably, it is 0.001-0.1 weight part.
When the compounding amount of the organic peroxide (G) exceeds 0.5 parts by weight, the molding processability and mechanical properties of the polypropylene resin composition are insufficient, or molding is performed using the polypropylene resin composition. The transparency and hue of the product obtained by processing may be deteriorated.
Further, the organic peroxide (G) may be used as it is, and impregnated powder (impregnated with propylene-ethylene random copolymer (component (A)) or propylene homopolymer (component (B)) powder ( Master batch). The powder of propylene-ethylene random copolymer (component (A)) or propylene homopolymer (component (B)) is a powdery propylene-ethylene random copolymer (component (A)) or propylene homopolymer. It is a powder of (component (B)). The average particle diameter of the powder is not particularly limited, but is preferably 100 μm to 1000 μm from the viewpoint of dispersibility. The impregnation amount of the organic peroxide (G) is not particularly limited, but a range of 1 to 20% by weight is preferable in terms of handling.
Temperature in production (polypropylene system) in which the organic peroxide (G) is blended to adjust the melt flow rate (MFR) measured at 230 ° C. of the polypropylene resin composition of the present invention to a range of 10 to 100 g / 10 min. The temperature at which the resin composition is melt-kneaded is 180 ° C. or higher. Preferably it is 200-300 degreeC, More preferably, it is the range of 200-260 degreeC. If it is less than 180 degreeC, the target melt flow rate (MFR) may not be adjusted, and when it exceeds 300 degreeC, the various characteristics of the polypropylene resin composition of this invention may deteriorate.

  The polypropylene resin composition of the present invention is a surface of a molded body (film, sheet, injection molded body, etc.) obtained using the polypropylene resin composition from the viewpoints of transparency, mechanical properties, appearance, and crystallization speed. It is preferable that the number of white spots generated in is small. As a method for calculating the number of white spots, a test piece molded by an injection molding method was sandwiched between both sides of the test piece with a polarizing plate, and the light from a fluorescent lamp was transmitted through the polarizing plate and the test piece. It is calculated | required by observing the white spot point which exists in visual observation visually. For example, when the number of white spots observed within a certain area (50 × 50 mm) in the central portion of the test piece is less than 5, ◯, when 5-10, Δ, when 10 or more, x, 50 When the number is more than XX and this is used as an index, it can be determined that the smaller the number of white spots, the more excellent the appearance.

Moreover, you may mix | blend a well-known additive with the polypropylene resin composition of this invention as needed. For example, neutralizers (hydrotalcite, alkyl earth oxides and hydroxides), antioxidants, UV absorbers, light stabilizers, antistatic agents, lubricants, antiblocking agents, processing aids, coloring Agents, foaming agents, antibacterial agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, brightening agents and the like. These additives may be used alone or in combination of at least two kinds. Of these, neutralizers, antioxidants, and colorants are often used.
Examples of the neutralizing agent include hydrotalcites, oxides or hydroxides of alkaline earth metals. These neutralizing agents may be blended for the purpose of neutralizing a chlorine compound that is a catalyst residue at the time of producing a polypropylene resin, and may be used alone or in combination of at least two kinds.
The hydrotalcite is an anion exchangeable layered compound. 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 the said hydrotalcite as needed.
Among the hydrotalcites represented by the above general formula, the hydrotalcite represented by the following formula (IV) is preferable.
_{Mg Y Al 2 (OH) 2Y} + 4 CO 3 · mH 2 O formula (IV)
(In the formula, Y is Y ≧ 4, and m is a positive number.)
More preferably, M ²⁺ in the general formula (IV) is composed of any one of Mg ²⁺ and Zn ²⁺ , or two divalent metal cations, and more preferably, Hydrotalcite.
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 (natural mineral)
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 compounding quantity of a neutralizing agent is 0.001-0.5 weight part with respect to 100 weight part of said resin mixtures (component (A), component (B), and component (C)), for example. Preferably it is 0.005-0.2 weight part, More preferably, it is 0.01-0.2 weight part.

Moreover, a well-known thing can be used for antioxidant, and with antioxidant, the heat | fever of the said resin component (component (A), component (B), and component (C)), light, oxygen, etc. It is a compound which has the effect | action which prevents decomposition | disassembly by. For example, phenolic antioxidants, phosphorus antioxidants, hydroxylamine antioxidants and the like can be mentioned, and among them, phenolic antioxidants and phosphorus antioxidants are often used alone or in combination.
Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol and tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate]. Methane, octadecyl-3- (3,5-di-tert-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, 1,3,5-tris 2 [3 (3,5-di-t-) Butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ben Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-N-bis-3- (3-tert-butyl-5-methyl-4-) Hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis-diethylenebis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2, '-Methylene-bis- (4-ethyl-6-tert-butylphenol), 2,2'-methylene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (4 , 6-di-tert-butylphenol), 2,2′-butylidene-bis- (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2 -T-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5- And di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and tocopherols. Examples of tocopherols include vitamin E, which is α-tocopherol.
The phenolic antioxidant is preferably 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-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis-diethylenebis [3- (3,5 Di-t-butyl-4-hydroxyphenyl) propionate], and more preferably, since a resin composition having excellent hue stability can be obtained, 3,9-bis [2- {3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.
The amount of the phenolic antioxidant is generally 0.01 to 2 parts by weight with respect to 100 parts by weight of the resin mixture (component (A), component (B) and component (C)). Preferably it is 0.01-1 weight part, More preferably, it is 0.01-0.5 weight part.
Examples of phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4- Di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4- Methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-diphenylenediphosphonite, 2, 2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2 , 2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,4) 6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5, 5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphite, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl- 4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine.
Preferably, since the processing stability of the polypropylene resin composition can be improved, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) penta Erythritol diphosphite, 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1 , 3,2] dioxaphosphepine.
The compounding amount of the phosphorus antioxidant is generally 0.01 to 2 parts by weight with respect to 100 parts by weight of the resin mixture (component (A), component (B) and component (C)). Preferably it is 0.01-1 weight part, More preferably, it is 0.01-0.5 weight part.

These additives can be blended, for example, by blending the resin components (component (A), component (B), and component (C)) previously melt-kneaded into pellets or polypropylene resin composition as pellets. The method of mix | blending together with each component ((D), (E), (F), (G)) in the step to convert is mentioned.
In the polypropylene resin composition of the present invention, if necessary, other resins or rubbers other than the resin components (component (A), component (B) and component (C)) used in the present invention are blended. May be.
For example, high density polyethylene (HDPE), low density polyethylene (LDPE), ethylene / α-olefin copolymer (L-LDPE or elastomer), polystyrenes (eg, polystyrene, poly (p-methylstyrene), poly (α -Methylstyrene), AS (acrylonitrile / styrene copolymer) 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, fluororesin, polyacetal, grafted polyphenylene ether resin and polyphenol Nylene sulfide resin, polyurethane, polyamide, polyester resin (eg, polyethylene terephthalate, polybutylene terephthalate), thermoplastic resin such as polycarbonate, polysulfone, polyether ether ketone, polyether sulfone, aromatic polyester resin, epoxy resin, diallyl phthalate prepolymer , Silicone resin, silicone rubber, polybutadiene, 1,2-polybutadiene, polyisoprene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, epichlorohydrin rubber, acrylic rubber, natural rubber, polylactic acid, etc. Other resins may be used alone or in combination of at least two kinds.
For example, the resin component (component (A), component (B) and component (C)) other than the resin, rubber, and the like may be blended into a polypropylene resin composition pellet that has been previously melt-kneaded. The method and the polypropylene resin (A) and each component ((D), (E), (F), (G)) and the additive added as necessary at the stage of producing the polypropylene resin composition The method of mix | blending together is mentioned.
In addition, the other resins and rubbers may be used by being laminated with the polypropylene resin composition of the present invention.

Moreover, you may mix | blend a filler with the polypropylene resin composition of this invention as needed in the range which does not impair the objective of this invention.
Examples of the filler include talc, clay, glass beads, calcium silicate, silica, zeolite, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, alumina, aluminum hydroxide, magnesium hydroxide, and basic carbonate. Examples include magnesium, calcium carbonate, magnesium carbonate, synthetic organic fiber, natural fiber, and wood flour.
Examples of the method of blending the filler include, for example, a method of blending into a pellet of a polypropylene resin composition melt-kneaded in advance, and a polypropylene resin component and each component ((D), (E), (F), (G)) and the method of mix | blending with the said additive added as needed is mentioned.
In the case where talc, clay or calcium carbonate is blended as the filler, 0.001 to 100 parts by weight of the resin mixture (component (A), component (B) and component (C)) When blending 1 part by weight of talc, clay, or calcium carbonate, talc, clay, or calcium carbonate functions as a nucleating agent, so it may be blended at the stage of producing a polypropylene resin composition.
Moreover, as a coloring agent, the well-known coloring agent generally used is mentioned, An inorganic pigment and an organic pigment are mentioned. As the inorganic pigment, for example, carbon black, iron oxide, titanium oxide, zinc oxide, petrol, cadmium red, cadmium yellow, ultramarine, cobalt blue, titanium yellow, lead white, lead red, Examples of the organic 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 at least two kinds.

As a method of blending the additive resin, other resin, rubber, filler, etc. added as necessary to the polypropylene resin composition of the present invention and melting and mixing at 180 ° C. or higher, for example, known melting The method of mixing is mentioned, The method of melt-mixing with a melt extruder, a Banbury mixer, etc. is mentioned.
Moreover, as a method of mix | blending each said component ((D), (E), (F), (G)) used by this invention, the said resin component (component (A), component ( B) and component (C)) and each component ((D), (E), (F), (G)) are melt-mixed to produce each component ((D), (E), (F) , (G)) a high-concentration masterbatch having a concentration of 1 to 90% by weight, and any one of each component ((D), (E), (F), (G)) and at least one kind Mix with other additives, solidify into granules, and prepare high-concentration granules in which the concentration of each component ((D), (E), (F), (G)) is 10 to 90% by weight. And the method of carrying out the dilution compounding to the said resin component (component (A), component (B), and component (C)) used by this invention is mentioned.
Examples of the melt-kneading apparatus used in the method for producing the polypropylene resin composition of the present invention include known melt-kneading apparatuses. For example, single-screw extruder, twin-screw co-rotating extruder (ZSK [registered trademark] manufactured by Wernw Pfleideren, TEM [registered trademark] manufactured by Toshiba Machine Co., Ltd., TEX [registered trademark] manufactured by Nippon Steel Works), etc.) , Twin screw different direction rotary extruder (CMP [registered trademark], TEX [registered trademark], manufactured by Nippon Steel Works, Ltd., FCM [registered trademark], NCM [registered trademark], LCM [registered trademark], manufactured by Kobe Steel, Ltd. Trademark]].
Examples of the shape of the polypropylene resin composition of the present invention 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 apply the polypropylene resin composition of the present invention to molding processing, 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 molded body of the present invention is a molded body obtained by molding the polypropylene resin composition of the present invention by various molding methods, and the shape, size, etc. of the molded body may be appropriately determined.
Examples of the method for producing the molded product of the present invention include injection molding methods, press molding methods, vacuum molding methods, foam molding methods, extrusion molding methods and the like that are usually used industrially, and depending on the purpose. Examples thereof include a molding method in which the same type of polyolefin resin as the polypropylene resin composition of the present invention and other resins are bonded, a method of coextrusion molding, and the like.
The molded body of the present invention is preferably an injection molded body, and the molding method is an injection molding method. Examples of injection molding methods include general injection molding methods, injection foam molding methods, supercritical injection foam molding methods, ultra-high speed injection molding methods, injection compression molding methods, gas assist injection molding methods, sandwich molding methods, sandwich foaming methods. Examples thereof include molding methods and insert / outsert molding methods.
Examples of uses of the molded article of the present invention include miscellaneous goods, household electrical appliance materials, OA equipment materials, medical materials, drain pans, toiletry materials, various bottles, containers, cups, sheets, films, and the like. Among these, it is preferable to form and process various bottles, cups, sheets, and films used as food containers and food packaging molded bodies. Examples of the bottle include bolts for drinking water, and examples of the cup include storage cups such as pudding, yogurt, and fruit jelly. The sheet can be secondarily processed into various containers by vacuum forming or the like and used for the same application as the cup. Examples of the film include stretched films for various packaging, unstretched films, inflation films, and the like, and can be used as food packaging materials.

  Hereinafter, the present invention will be described by way of examples. The measuring method of the physical property of the polymer used in the Example and the comparative example and the composition was shown below.

(1) Melt flow rate (MFR, unit: g / 10 minutes)
(1-1) Method for measuring MFR of propylene-ethylene random copolymer (component (A)) and propylene homopolymer (component (B)) Measured according to JIS-K6758 at a measurement temperature of 230 ° C. and a load of 2.16 kgf. did.
(1-2) Measurement of MFR of ethylene-based copolymer (component (C)) Measurement was carried out according to JIS-K7210 at a measurement temperature of 190 ° C. and a load of 2.16 kgf.
(2) Flexural modulus (unit: MPa)
It measured according to the method prescribed | regulated to JIS-K-7203. Using a test piece having a thickness of 6.4 mm and a span length of 100 mm formed by injection molding described later, the load speed was 2.5 mm / min, and the measurement temperature was 23 ° C. The flexural modulus is an index of stiffness, and the larger the flexural modulus, the better the stiffness.
(3) Ethylene content (unit: wt%)
The content of ethylene-derived structural units was measured using an IR spectrum in accordance with the method described in the section of “(i) Random copolymer” on page 256 of Polymer Analysis Handbook (published by Asakura Shoten in 1985).
(4) Crystallization rate (crystallization time, unit: seconds)
The measurement was performed using “Diamond DSC” (differential scanning calorimeter) manufactured by PerkinElmer Japan Co., Ltd. Specifically, the polypropylene 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, the temperature was rapidly cooled to a predetermined temperature at a rate of 300 ° C./min, and the temperature was maintained at the predetermined temperature until the time corresponding to the end of the caloric curve. The crystallization time was determined as the time (seconds) required to reach the maximum value (peak top) of the obtained heat quantity curve. In addition, the time required for crystallization is shorter as the required time is shorter. The shorter the crystallization time, the shorter the cooling time during the molding process, and the better the moldability.
(5) Impact resistance (falling weight impact strength (FWI), unit: J)
The shape of the weight used for the measurement is shown in FIG. Except for using an iron weight having the shape shown in FIG. 1, the impact energy when 50% of the number of test pieces breaks was determined according to the measurement method of JIS K7211. The measurement temperature was 23 ° C.
In addition, what was obtained by the manufacturing method of the injection molded body mentioned later was used for the test piece. Specifically, the test piece used was obtained by injection molding described later. Specifically, a long flat test piece of MD × TD × thickness = 150 × 90 × 2 mm was used.
(6) Transparency (haze, unit:%)
It measured according to JIS K7150. The test piece was obtained by injection molding described later (MD × TD × thickness = 150 × 90 × 2 mm long flat plate test piece with the central portion cut into a 50 × 50 mm square). A haze meter was used for haze measurement. The haze value is an index of transparency. The smaller the haze value, the better the transparency of the test piece as viewed with the eye, and the higher the transparency.
(7) White spot (visual)
About the test piece (MD × TD × thickness = 150 × 90 × 2 mm) molded by the injection molding method, the polarizing plate is sandwiched from both sides, the light from the fluorescent lamp is transmitted, and the white spots existing on the test piece are visually observed. Observed with. In the judgment, the case where the number of white spots was less than 5 was evaluated as ◯, the case where it was less than 5 to 10, and the case where it was 10 or more as x. The white spot is an index indicating the dispersibility of the additive component including the nucleating agent component, and the smaller the number of white spots, the more excellent the appearance.
(8) Odor A test piece (MD × TD × thickness = 150 × 90 × 2 mm) molded by an injection molding method to be described later was subjected to a human odor sensory test to determine the presence or absence of the unpleasant odor. Judgment was made when there was no unpleasant odor, and when there was yes.
(9) Production of injection-molded body The test pieces (injection-molded bodies) for the above-mentioned mechanical property evaluation, drop weight impact strength evaluation, and transparency evaluation were prepared according to the following method.
(1) Preparation of test specimen for mechanical property evaluation Using a NEOMAT 350/120 type injection molding machine manufactured by Sumitomo Heavy Industries, injection molding was performed at a molding temperature of 220 ° C and a mold cooling temperature of 50 ° C, and a test piece for mechanical property evaluation. Got.
(2) Production of test piece for drop weight impact strength evaluation Using a NEOMAT 350/120 type injection molding machine manufactured by Sumitomo Heavy Industries, injection molding is performed at a molding temperature of 220 ° C. and a mold cooling temperature of 50 ° C., MD × TD × thickness = Test pieces for evaluating drop weight impact strength and for evaluating transparency having dimensions of 150 × 90 × 2 mm were obtained.

Reference example 1
(1-1) Production of solid catalyst component The solid catalyst component was prepared in the same manner as described in Example 1 of JP-A No. 2004-067850.
(1-2) Production of polypropylene resin (A-1) (a) Prepolymerization After fully purified hexane was added to a reactor equipped with a stirrer and the system was sufficiently replaced with nitrogen, triethylaluminum (hereinafter referred to as TEA) Abbreviation), cyclohexylethyldimethoxysilane (hereinafter abbreviated as CHEDMS) and the solid catalyst component were added, and propylene was continuously added over 1 hour while maintaining 25 ° C. to obtain a prepolymer slurry.
(B) Using a gas phase fluidized bed polymerization tank equipped with a polymerization stirrer, the polymerization temperature is 83 ° C., the polymerization pressure is 21 kg / cm ² G, and the ethylene concentration in the gas phase is 1.35 vol. %, The hydrogen concentration is 4.0 vol. %, The prepolymer slurry, TEA (TEA / propylene polymer = 200 wtppm), CHEDMS (CHEDMS / TEA = 0.15 (mol / mol)) under the conditions of supplying propylene, ethylene and hydrogen. Gas phase polymerization was carried out while supplying propylene-ethylene copolymer powder (A-1). The resulting propylene-ethylene copolymer (A-1) had a melting point (Tm) of 148 ° C., an ethylene content of 2.5% by weight, CXS of 2.5% by weight, and MFR of 25 g / 10 min. It was.

Reference example 2
Production of Polypropylene Resin (A-2) (b) Production of Polypropylene Resin (A-1) in Reference Example 1 (b) In the main polymerization, polymerization temperature, polymerization pressure, ethylene concentration in the gas phase, hydrogen concentration The powder (A-2) of a propylene-ethylene random copolymer was obtained in the same manner as in the method for producing the (1-2) polypropylene resin (A-1) in Reference Example 1 except that the production was changed. The obtained propylene-ethylene random copolymer had a melting point (Tm) of 141 ° C., an ethylene content of 3.6% by weight, CXS of 3.0% by weight, and MFR of 25 g / 10 minutes.

Reference example 3
Polymerization of propylene homopolymer (B-1) In (1-2) (b) main polymerization of Reference Example 1, the ethylene concentration in the gas phase was changed to zero, the polymerization temperature was 86 ° C, and the hydrogen concentration was 2.2 vol. . The propylene homopolymer (B-1), which is a resin powder, was obtained in the same manner as in Reference Example 1 except that the percentage was changed to%. The obtained propylene homopolymer had a melting point (Tm) of 163 ° C., CXS of 0.25 wt%, and MFR of 20 g / 10 min.

Example 1
(1-1) Production of polypropylene resin composition [granulation (melt kneading, filtration)]
79 parts by weight of (A-1) propylene-ethylene random copolymer powder obtained in Reference Example 1 and 13 parts by weight of (B-1) propylene homopolymer powder obtained in Reference Example 3 (C -1) 8 parts by weight of pellets of polyethylene polymer (Excellen VL400 manufactured by Sumitomo Chemical Co., Ltd., 190 ° C. melt flow rate: 5 g / 10 min, density: 0.900 g / cm ³ ) were mixed. (D-1) 1,3: 2,4-bis-O-benzylidene-D-glucitol (trade name: Gelol D, manufactured by Shin Nippon Rika Co., Ltd.) 0.35 weight with respect to 100 parts by weight of this mixture And (E-1) disodium = (1R, 2R, 3S, 4S) -bicyclo [2.2.1] heptane-2,3-dicarboxylate as a main component (main component: 80% by weight) Contained, trade name: Hyperform HPN-68L, manufactured by Milliken Japan Co., Ltd.) 0.01 parts by weight and (F-1) calcium stearate (trade name: calcium stearate S, manufactured by Nippon Oil & Fats Co., Ltd.) 0.05 Parts by weight and (F-2) sodium stearate (NONSAL SN-1 powder, manufactured by NOF Corporation) and (G-1) 2,5-dimethyl-2,5-di (t- Butyl peroxy) hexa 10 wt% polypropylene powder (trade name: Perhexa 25B-10, 10 wt% product (manufactured by NOF Corporation) 0.05 parts by weight (0.005 parts by weight as an organic peroxide), and oxidation Tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name: Irganox 1010, manufactured by Ciba Specialty Chemicals) as an inhibitor 0.01 All parts by weight were mixed together and the mixture was mixed with a tumbler mixer, and the resulting mixture was set in a cylinder set temperature of the melt-kneading part using a single-screw extruder (manufactured by Tanabe Plastics Co., Ltd.) having an inner diameter of 40 mm. It is melt-kneaded under the conditions of 200 ° C., screw rotation speed 100 rpm, extrusion rate: 16 kg / hour, and this is filtered with a wire mesh filter (50 mesh). After that, extrusion was performed from the die part (setting: 200 ° C.), and this extrudate (strand shape) was cooled and solidified with cold water and cut into pellets (diameter: 2 to 3 mm) made of a polypropylene resin composition. Table 1 shows the amount of each component of the resin composition.
(1-2) Manufacture of a polypropylene resin composition A test for evaluating physical properties by injection molding using a pellet made of the polypropylene resin composition manufactured by the method of (1-1) according to the method for manufacturing an injection molded body. A piece was prepared, and after adjusting a predetermined state, the physical properties of the test piece were measured. The evaluation results are shown in Table 1.

Example 2
(A-2) propylene-ethylene random copolymer powder 79 parts by weight obtained in Reference Example 2 and (B-1) propylene homopolymer powder 13 parts by weight obtained in Reference Example 3 (C -1) 8 parts by weight of polyethylene polymer pellets were mixed. The same procedure as in Example 1 was performed except that the mixture was changed to 100 parts by weight. The evaluation results are shown in Table 1.

Example 3
It carried out like Example 1 except not having blended (F-2). The evaluation results are shown in Table 1.

Example 4
The same procedure as in Example 1 was performed except that (D-1) was changed to 0.30 parts by weight, (E-1) to 0.02 parts by weight, and (F-2) to 0.036 parts by weight. The results are shown in Table 1.

Example 5
The same procedure as in Example 1 was performed except that (D-1) was changed to 0.30 parts by weight and (F-2) was changed to 0.009 parts by weight. The results are shown in Table 1.

Example 6
(D-1) was changed to 0.30 parts by weight, (E-1) was changed to 0.02 parts by weight, (F-2) was not blended, and (G-1) was not blended. The same operation as in Example 1 was performed. The results are shown in Table 1.

Example 7
Example 1 except that (A-1) was changed to 86 parts by weight, (B-1) to 10 parts by weight, (C-1) to 4 parts by weight, and (G-1) to 0.03 parts by weight. As well as. The results are shown in Table 1.

Example 8
(A-1) was changed to (A-2) 88 parts by weight, (B-1) to 10 parts by weight, (C-1) to 2 parts by weight, and (G-1) to 0.02 parts by weight. Was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 9
67 parts by weight of (A-1), 25 parts by weight of (B-1), 0.30 parts by weight of (D-1), 0.02 parts by weight of (E-1), and (F-2) The same procedure as in Example 1 was conducted except that (G-1) was changed to 0.04 parts by weight without blending. The results are shown in Table 1.

Comparative Example 1
It carried out like Example 1 except not having blended (E-1) and (F-2). The evaluation results are shown in Table 2.

Comparative Example 2
The same procedure as in Example 1 was performed except that (D-1) was changed to 0.5 parts by weight and (E-1) and (F-2) were not blended. The evaluation results are shown in Table 2.

Comparative Example 3
0.35 parts by weight of (D-1) (D-2) (Millad 3988, manufactured by Milliken Japan Co., Ltd., chemical name: 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol, apparent Bulk specific gravity: 0.20 g / cc; comparative product) The same procedure as in Example 1 was performed except that (E-1) and (F-2) were not blended. The evaluation results are shown in Table 2.

Comparative Example 4
(D-1) and (F-2) were not blended, and (E-1) was carried out in the same manner as in Example 1 except that 0.01 part by weight was changed to 0.35 part by weight. The evaluation results are shown in Table 2.

Comparative Example 5
(D-1) and (F-2) were not blended, and the same procedure as in Example 1 was performed except that (E-1) 0.01 parts by weight was changed to 0.02 parts by weight. The evaluation results are shown in Table 2.

Comparative Example 6
87 parts by weight of (A-1), (C-1), (F-2) are not blended, (D-1) is 0.3 parts by weight, and (E-1) is 0.02 parts by weight. The procedure was the same as in Example 1 except for the change. The evaluation results are shown in Table 2.

Comparative Example 7
92 parts by weight of (A-1), (B-1) and (F-2) are not blended, (D-1) is 0.3 parts by weight, and (E-1) is 0.02 parts by weight. The procedure was the same as in Example 1 except for the change. The evaluation results are shown in Table 2.

Comparative Example 8
(A-1) is 87 parts by weight, (B-1) is 5 parts by weight, (F-2) is not blended, (D-1) is 0.3 parts by weight, and (E-1) is 0. The procedure was the same as Example 1 except that 02 parts by weight and (G-1) was changed to 0.04 parts by weight. The evaluation results are shown in Table 2.

Comparative Example 9
85 parts by weight of (A-1), 10 parts by weight of (B-1), 5 parts by weight of (C-1), (D-3) aromatic phosphate ester metal instead of (D-1) Nucleating agent based on salt (Adeka Stub NA-21, manufactured by ADEKA Corporation); comparative product) 0.2 parts by weight, (E-1) and (F-2) not blended, (G-1 ) Was changed to 0.08 parts by weight, and was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 10
(D-1) 0.3 parts by weight, (F-2) was not blended, (E-1) 0.01 parts by weight was changed to (E-2) 0.02 parts by weight of sodium benzoate Was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 11
(C-1) (C-2) Sumikasen G701 (manufactured by Sumitomo Chemical Co., Ltd., MFR (190 ° C.) = 7 g / 10 min, density = 0.918 g / cm ³ ; comparative product) 8 parts by weight, (D-1) 0.3 parts by weight, (E-1) 0.02 parts by weight, (F-2) was not blended, and (G-1) was changed to 0.04 parts by weight. The same was done. The evaluation results are shown in Table 2.

Comparative Example 12
(C-1) (C-3) Excellen VL100 (manufactured by Sumitomo Chemical Co., Ltd., MFR (190 ° C.) = 0.8 g / 10 min, density = 0.900 g / cm ³ ; comparative product) 8% by weight, (D- The same procedure as in Example 1 was performed except that 1) was changed to 0.3 parts by weight, (E-1) was changed to 0.02 parts by weight, and (F-2) was not added. The evaluation results are shown in Table 2.

It is a figure which shows the shape of the weight used for a measurement of impact resistance (falling weight impact strength).

Claims (4)

The following propylene-ethylene random copolymer (component (A)) 50 to 91% by weight, the following propylene homopolymer (component (B)) 7 to 30% by weight, and the following ethylene copolymer (component (C)) ) 2-20% by weight of a resin mixture (component (A), component (B) and component (C) is 100% by weight in total), and 100 parts by weight of the resin mixture,
The following general formula (I)

Represented by (formula (in I), represent the R ¹ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, -C 1-8 alkyl or -C 1-4 alkoxy group.) At least one dibenzylidene sorbitol (D) 0.05-2 parts by weight;
The following general formula (II)

(In the formula (II), M ₁ and M ₂ are each selected from the group consisting of a sodium atom and a hydrogen atom, wherein at least one of M ₁ and M ₂ is a sodium atom, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each hydrogen, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, or 1 to 9 carbon atoms. Alkoxy group, alkyleneoxy group having 1 to 9 carbon atoms, amino group, alkylamine group having 1 to 9 carbon atoms, halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), and phenyl group Wherein, when these groups are alkyl groups, the alkyl groups may combine to form a carbocyclic ring having up to 6 carbon atoms, the compound having a trans or cis configuration Either At least one metal salt (E) represented by cis configuration, and 0.001 to 0.5 parts by weight,
The following general formula (III)

(In the formula (III), R ²¹ represents a group introduced from an aliphatic organic acid having 10 to 30 carbon atoms, M ³ represents an alkali metal atom, an alkaline earth metal atom or a zinc atom, and n represents 1 or 2). A polypropylene resin composition comprising 0 to 1 part by weight of at least one aliphatic organic acid metal salt (F).
Ingredient (A):
The content of structural units derived from ethylene is 2 to 5% by weight,
Propylene-ethylene random copolymer having a melt flow rate (JIS-K6758) measured at a measurement temperature of 230 ° C. and a load of 2.16 kgf of 2 to 90 g / 10 minutes (however, the total amount of propylene-ethylene random copolymer is 100 %).
Ingredient (B):
A propylene homopolymer having a melt flow rate (JIS-K6758) measured at a measurement temperature of 230 ° C. and a load of 2.16 kgf of 2 to 150 g / 10 minutes.
Component (C):
Propylene having a density of 0.86 to 0.91 g / cm ³ , a melt flow rate (JIS-K7210) measured at a measurement temperature of 190 ° C. and a load of 2.16 kgf of 2 to 100 g / 10 min, and a carbon number of 4 A copolymer obtained by copolymerizing at least one olefin selected from -18 α-olefins and ethylene.   2. The polypropylene according to claim 1, wherein the melt flow rate (MFR) measured at 230 ° C. modified by melt mixing in the presence of the organic peroxide (G) is 10 to 100 g / 10 minutes. Resin composition.   A molded article comprising the polypropylene resin composition according to claim 1.   A food filling container or a food packaging molded article comprising the polypropylene resin composition according to any one of claims 1 to 3.

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