JP2009155422A - Polypropylene resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene resin composition which enables to obtain a molded article having improved surface impact resistance and transparency, and reduced odor emission rate and elution property, and to provide a molded article comprising the resin composition. <P>SOLUTION: The polypropylene resin composition is prepared by blending a specific compound (D) in 100 pts.mass of a resin mixture comprising 50-91 mass% of a specific propylene-ethylene random copolymer (A), 7-30 mass% of a specific propylene homopolymer (B), and 2-20 mass% of a specific ethylene copolymer (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  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 resin composition used for such applications, for example, Patent Document 1 discloses an ethylene / α-olefin copolymer polymerized using a specific propylene / ethylene random copolymer and a specific metallocene catalyst, and A polypropylene resin composition obtained by adding an organic peroxide to a mixture containing a specific propylene homopolymer and melt-mixing the mixture is described.

Patent Document 2 discloses a polypropylene resin composition obtained by blending a specific polypropylene resin with an ethylene / α-olefin copolymer having a refractive index difference in a specific range with a specific ratio. Is described.
Patent Document 3 describes a polypropylene resin composition obtained by blending a polypropylene resin with a polyolefin rubber having a specific refractive index and a specific transparent nucleating agent.
Patent Document 4 describes a polypropylene resin composition comprising a specific polypropylene resin and a specific ethylene copolymer and a sorbitol nucleating agent.
Patent Document 5 describes a polypropylene resin composition comprising a propylene polymer comprising a specific ethylene (co) polymer and another ethylene polymer.
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, in molded articles obtained by using the polypropylene resin composition described in the above publication, further improvements in surface impact and transparency and further reduction in odor and elution are required. Moreover, when manufacturing a molded object, it is desired that the crystallization rate of the said resin composition is quick and a molding cycle can be shortened and productivity is improved.
Under such circumstances, the present invention provides a polypropylene resin composition capable of obtaining a molded article with improved surface impact and transparency, and reduced odor and elution, and a molded article comprising the same. Objective. Also, when producing a molded article, it is possible to provide a polypropylene resin composition capable of increasing the crystallization speed of the resin composition, shortening the molding cycle, and improving productivity, and a molded article comprising the same. Objective.

〔式中、ｎは、０、１又は２であり、Ａは非水素基であり、Ｒ₁〜Ｒ₁₀は、互いに独立して、水素、フルオロ炭素、アルキル基、アルキニル基、アルケニル基、アルコキシ基、カルボキシ基、ハロゲン基、及びフェニル基からなる群から選択され、任意の二つの隣接基は、組み合わさって環式基を形成しても良い〕
成分（Ａ）：
エチレン由来の構造単位の含有量が２〜５質量％であり、
測定温度２３０℃、荷重２．１６ｋｇｆで測定したメルトフローレート（ＪＩＳ−Ｋ６７５８）が２〜９０ｇ／１０分であるプロピレン−エチレンランダム共重合体（ただし、プロピレン−エチレンランダム共重合体の全量を１００質量％とする）。
成分（Ｂ）：
測定温度２３０℃、荷重２．１６ｋｇｆで測定したメルトフローレート（ＪＩＳ−Ｋ６７５８）が２〜１５０ｇ／１０分であるプロピレン単独重合体。
成分（Ｃ）：
密度が０．８８〜０．９１ｇ／ｃｍ³であり、測定温度１９０℃、荷重２．１６ｋｇｆで測定したメルトルフローレート（ＪＩＳ−Ｋ７２１０）が２〜１００ｇ／１０分であるプロピレン及び炭素数４〜１８のα−オレフィンから選ばれる少なくとも１種のオレフィンとエチレンと共重合させて得られる共重合体。 As a result of intensive studies, the present inventors have found that the above problem can be solved by adopting the following configuration, and have completed the present invention.
That is, the present invention
The following propylene-ethylene random copolymer (component (A)) 50 to 91% by mass, the following propylene homopolymer (component (B)) 7 to 30% by mass, and the following ethylene copolymer (component (C)) ) A resin mixture containing 2 to 20% by mass (the total of component (A), component (B) and component (C) is 100% by mass), and 100 parts by mass of the resin mixture,
The present invention provides a polypropylene-based resin composition comprising 0.12 to 0.5 parts by mass of at least one compound (D) represented by the following general formula.

[Wherein n is 0, 1 or 2; A is a non-hydrogen group; and R _{1 to} R ₁₀ are independently of each other hydrogen, fluorocarbon, alkyl group, alkynyl group, alkenyl group, alkoxy group. Selected from the group consisting of a group, a carboxy group, a halogen group, and a phenyl group, and any two adjacent groups may be combined to form a cyclic group.
Ingredient (A):
The content of structural units derived from ethylene is 2 to 5% by mass,
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 Mass%).
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 0.88 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.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the polypropylene-type resin composition which can obtain the molded object which surface impact property and transparency improved, and the odor and the elution property were reduced, and a molded object consisting thereof. . Further, when producing a molded article, it is possible to provide a polypropylene resin composition capable of increasing the crystallization speed of the resin composition, shortening the molding cycle, and improving the productivity, and a molded article comprising the same. It becomes possible.

The polypropylene resin composition according to the present invention contains a resin mixture containing components (A) to (C) and a compound (D). This will be described in detail below.
[Propylene-ethylene random copolymer (component (A))]
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 mass (provided that propylene-ethylene is used). The total amount of the random copolymer is 100% by mass). The content of the structural unit derived from ethylene is preferably 2 to 4% by mass.
When the content of the structural unit derived from ethylene is less than 2% by mass, the surface impact property may be insufficient, and when it exceeds 5% by mass, 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 mass (the total of the component (A), the component (B) and the component (C) is 100% by mass), Preferably it is 70-91 mass%. When the content of the component (A) is less than 50% by mass, sufficient transparency and surface impact may not be obtained. When it exceeds 91% by mass, a sufficient crystallization rate cannot be obtained and molding is performed. Cycle performance may not be shortened sufficiently.

[Propylene homopolymer (component (B))]
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 130 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 (mmmm) measured by ¹³ C-NMR of the component (B) is preferably 0.95 or more from the viewpoint of increasing rigidity, heat resistance or crystallization time, Preferably, it is 0.97 or more.

The isotactic pentad fraction is defined as A.I. The method published in Macromolecules, 6, 925 (1973) by Zambelli et al., Ie isotactic linkage in pentad units in a polypropylene molecular chain measured using ¹³ C-NMR, in other words propylene monomer units Is the fraction of units derived from the propylene monomer at the center of the chain of five consecutive meso-bonded chains (however, the assignment of the NMR absorption peak is based on 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. By this method, NPL reference material CRM No. of NATIONAL PHYSICAL LABORATORY, UK When the isotactic pentad fraction of M19-14 Polypropylene PP / MWD / 2 was measured, it was 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.

  Moreover, content of a component (B) is 7-30 mass% (The sum total of a component (A), a component (B), and a component (C) is 100 mass%), Preferably it is 10-25 mass%. is there. When the content of the component (B) is less than 7% by mass, a sufficient crystallization rate may not be obtained or the impact resistance may be inferior. When it exceeds 30% by mass, sufficient transparency and impact resistance are obtained. Sexuality may not be obtained.

[Polyethylene copolymer (component (C))]
The polyethylene 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 resistance are 0.88~0.91g / cm ^3, preferably 0.89~0.91g / cm ^3. When the density is 0.88 g / cm ³ or less, the transparency may be insufficient, and when it exceeds 0.91 g / cm ³ , the 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. Moreover, content of (C) is 2-20 mass% (The sum total of a component (A), a component (B), and a component (C) is 100 mass%), Preferably it is 4-10 mass%. . When the content of the component (C) is less than 2% by mass, sufficient impact resistance may not be obtained. When the content exceeds 20% by mass, a sufficient crystallization rate cannot be obtained, and the molding cycle property is low. It may not be shortened sufficiently.

〔式中、ｎは、０、１又は２であり、Ａは非水素基であり、Ｒ₁〜Ｒ₁₀は、互いに独立して、水素、フルオロ炭素、アルキル基、アルキニル基、アルケニル基、アルコキシ基、カルボキシ基、ハロゲン基、及びフェニル基からなる群から選択され、任意の二つの隣接基は、組み合わさって環式基を形成しても良い〕 [Compound (D) (Component (D))]
The compound (D) used in the present invention is at least one compound represented by the following general formula.

[Wherein n is 0, 1 or 2; A is a non-hydrogen group; and R _{1 to} R ₁₀ are independently of each other hydrogen, fluorocarbon, alkyl group, alkynyl group, alkenyl group, alkoxy group. Selected from the group consisting of a group, a carboxy group, a halogen group, and a phenyl group, and any two adjacent groups may be combined to form a cyclic group.

The non-hydrogen group A includes —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₂ CH ₃ , —CH ₂ CH═CH ₂ , —CH (CH ₃ ) CH═ CH ₂ , —CH ₂ CH—X—CH ₂ —X ′, CH ₂ CH—X ″ —CH ₂ —CH ₃ , —CH ₂ CH—X ′ ″ — CH ₂ OH, and CH—OH—CH Selected from —OH—CH ₂ —OH, wherein X, X ′, X ″, and X ′ ″ comprise independently selected halogen groups. Here, as a halogen group, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably they are a chlorine atom and a bromine atom.
In the formula, R _{1 to} R ₁₀ are independently selected from the group consisting of hydrogen, fluorocarbon, alkenyl, alkyl group, alkynyl group, alkoxy group, carboxy group, halide, and phenyl, or In some embodiments of the invention, any two adjacent groups can be combined to form a cyclic group. Here, the cyclic group may comprise methylenedioxy, cyclopentyl, cyclohexyl, or other similar cyclic group.

  Examples of the compound (D) used in the present invention include (but are not limited to) 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol, bis -1,3: 2,4- (4'-ethylbenzylidene) 1-allylsorbitol, bis-1,3: 2,4- (5 ', 6', 7 ', 8'-tetrahydro-2-naphthaldehyde Benzylidene) 1-allylxylitol, bis-1,3: 2,4- (3 ′, 4′-dimethylbenzylidene) 1-propylxylitol, bis-1,3: 2,4- (3′-methyl-4 ′ -Fluoro-benzylidene) 1-propylsorbitol, bis-1,3: 2,4- (3 ′, 4′-dimethylbenzylidene) 1′-methyl-2′-propenylsorbitol, bis-1,3,2,4 -Dibenzylidene 2 ', 3'-dibromopropylsorbitol, Bis-1,3,2,4-dibenzylidene 2'-bromo-3'-hydroxypropylsorbitol, bis-1,3: 2,4- (3'-bromo-4'-ethylbenzylidene) -1-allyl Sorbitol, mono 2,4- (3′-bromo-4′-ethylbenzylidene) -1-allyl sorbitol, bis-1,3: 2,4- (4′-ethylbenzylidene) 1-allyl sorbitol, bis-1 , 3: 2,4- (3 ′, 4′-dimethylbenzylidene) 1-methylsorbitol and the like.

The compounding quantity of the compound (D) used by this invention is 0.12-0.5 mass part with respect to 100 mass parts of the said resin mixture (component (A), component (B), and component (C)). Yes, preferably 0.15-0.5 parts by mass, more preferably 0.2-0.4 parts by mass. When the compounding amount of the compound (C) is less than 0.12 parts by mass, the effect of improving the transparency, mechanical strength and molding processability is insufficient, and when it exceeds 0.5 parts by mass, the resin component Dispersibility with respect to (component (A), component (B) and component (C)) may deteriorate and mechanical properties such as impact resistance may deteriorate, and the effect of improving transparency may be saturated. There is sex.
The compound (D) is preferably used as a powder. The powder characteristics preferably have an apparent bulk specific gravity 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 obtained by calculation by measuring the weight of the compound (D) powder when the compound (D) powder is laminated in a constant volume by a natural drop in a constant volume. Is. 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)) will be reduced. 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 a compound (D), a well-known manufacturing method is mentioned. Examples of the method for producing the powder of the compound (D) include a pulverization method and a method of producing by changing the precipitation conditions during the particle production process. In order to prevent aggregation of particles during the production, surface treatment is performed. You may manufacture in the state which contacted the agent, surfactant, etc.

The melt flow rate (MFR) of the polypropylene resin composition of the present invention is preferably 10 to 100 g / 10 min, more preferably 20 to 50 g / min, from the viewpoint of improving moldability, ductility and impact resistance. 10 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 for adjusting the melt flow rate (MFR) measured at 230 ° C. to a range of 10 to 100 g / 10 minutes, a propylene-ethylene random copolymer (component (A )), Propylene homopolymer (component (B)), ethylene copolymer (component (C)) and component (D), and further modified by melt mixing in the presence of organic peroxide (E). Can be adjusted.

[Organic peroxide (E) (component (E))]
The polypropylene resin composition of the present invention may contain an organic peroxide (E). Examples of the organic peroxide (E) include alkyl peroxides, diacyl peroxides, peroxide esters, and 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, dicetylperoxydicarbonate, dimyristylperoxydicarbonate and the like.
The organic peroxide (E) is preferably an alkyl peroxide, and particularly preferably 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butyl). Peroxyisopropyl) benzene, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan.

The compounding quantity of an organic peroxide (E) is 0-0.5 mass part with respect to 100 mass parts of said resin mixtures (component (A), component (B), and component (C)). Preferably it is 0.0005-0.3 mass part, More preferably, it is 0.001-0.1 mass part.
By setting the blending amount of the organic peroxide (E) to 0.5 parts by mass or less, the moldability and mechanical properties of the polypropylene resin composition according to the present invention can be further improved. Moreover, it becomes possible to improve the transparency and hue of the molded article obtained.

  Further, the organic peroxide (E) may be used as it is, impregnated powder impregnated with powder of propylene-ethylene random copolymer (component (A)) or propylene homopolymer (component (B)) ( 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 (E) is not particularly limited, but a range of 1 to 20% by mass is preferable in terms of handling.

  Temperature in production (polypropylene) in which the organic peroxide (E) 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.

  Moreover, you may mix | blend a well-known additive with the polypropylene resin composition of this invention as needed. For example, neutralizers, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, antiblocking agents, processing aids, colorants, foaming agents, antibacterial agents, plasticizers, flame retardants, crosslinking agents, Examples thereof include a crosslinking aid and a brightening agent. These additives may be used alone or in combination of at least two kinds. Of these, neutralizers, antioxidants, and colorants are often used.

  Moreover, a well-known thing can be used for antioxidant, and an antioxidant is 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 the 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.

These additives may be blended, for example, by blending the resin components (component (A), component (B), and component (C)) pellets previously melt-kneaded, or by pelletizing a polypropylene resin composition. The method of mix | blending with a component (D) and the component (E) as needed 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 are blended into a polypropylene resin composition pellet previously melt-kneaded. The method and the method of mix | blending with a polypropylene resin (A), a component (D), and a component (E), the said additive, etc. as needed at the stage which manufactures a polypropylene resin composition are mentioned.
The other resins and rubbers can 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.
As a method of blending the filler, for example, a method of blending into a pellet of a polypropylene resin composition melt-kneaded in advance, or a polypropylene resin component and each component ((D ), (E)) and a method of blending together with the additive added as necessary.
In the case where talc, clay or calcium carbonate is blended as the filler, 0.001 to 100 parts by mass of the resin mixture (component (A), component (B) and component (C)). When 1 part by mass of talc, clay, or calcium carbonate is blended, talc, clay, or calcium carbonate functions as a nucleating agent, and 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.

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 sundries, household electrical appliance materials, OA equipment materials, medical materials, physics and chemistry equipment, 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 and composition used by the Example and the comparative example 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) Ethylene content (unit: mass%)
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).

(3) Crystallization rate (crystallization time, unit: seconds)
The measurement was performed using “Diamond DSC” (differential scanning calorimeter) manufactured by PerkinElmer Japan Co., Ltd. Specifically, a sample for measurement was prepared by forming pellets of a polypropylene resin composition into a film (100 μm) using a compression molding machine. 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 135 ° C. at a rate of 300 ° C./min, and the temperature was maintained until a corresponding time when the caloric curve was completed. 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.

(4) Surface impact properties (falling weight impact strength (FWI), unit: kgcm)
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.

(5) 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.

(6) 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.

(7) 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.

(8) Dissolution The test was conducted according to the Japanese Pharmacopoeia General Test Method (1996) and the Plastic Container Test Method for Infusion (7) Dissolution Test. In the ultraviolet absorption spectrum of the test solution, the absorbance at a wavelength of 220 nm to less than 241 nm is 0.08 or less, and / or the absorbance at a wavelength of 241 nm to 350 nm is 0.05 or less, and the absorbance in the wavelength range is The case where it was equal to or more than the above value was marked as x.

(9) Production of injection molded body The test pieces (injection molded body) for evaluating the falling weight impact strength and for evaluating the transparency were produced according to the following method.
(9-1) Manufacture of test pieces for falling weight impact strength evaluation and transparency 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 = 150 × 90 × 2 mm test pieces for falling weight impact strength evaluation and transparency evaluation 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-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) Main polymerization Using a gas phase fluidized bed polymerization tank equipped with a stirrer, the polymerization temperature is 83 ° C., the polymerization pressure is 21 kg / cm ² G, 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 mass, CXS of 2.5% by mass, 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 140 ° C., an ethylene content of 4.1% by mass, CXS of 4.3% by mass, and MFR of 8 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 mmmm of 0.98, an Mw / Mn of 4.2, a melting point (Tm) of 163 ° C., a CXS of 0.25% by mass, and an MFR of 20 g / 10 min.

[Reference Example 4]
Polymerization of propylene homopolymer (B-2) Propylene homopolymer (B-2), which is a resin powder, was produced by a gas phase polymerization method using the solid catalyst component described in JP-A-7-216017. The obtained propylene homopolymer had a mmmm of 0.97, Mw / Mn of 5.9, a melting point (Tm) of 164 ° C., CXS of 1.1% by mass, and MFR of 120 g / 10 min.

[Reference Example 5]
Polymerization of propylene homopolymer (B-3) Propylene homopolymer (B-3), which is a resin powder, was produced by a solvent polymerization method using the solid catalyst component described in JP-A-7-216017. The mmmm was 0.99, the Mw / Mn was 5.3, the melting point (Tm) was 163 ° C., the CXS was 0.1% by mass, and the MFR was 307 g / 10 min.

[Example 1]
(1-1) Production of polypropylene resin composition [granulation (melt kneading, filtration)]
79 parts by mass of (A-1) propylene-ethylene random copolymer powder obtained in Reference Example 1 and 13 parts by mass of (B-1) propylene homopolymer powder obtained in Reference Example 3 (C -1) 8 parts by mass 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) 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol (trade name: Millad NX8000, Milliken with respect to 100 parts by mass of this mixture (Japan Co., Ltd.) 0.3 parts by mass and (E-1) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane containing 10% by mass of polypropylene powder (trade name: Perhexa 25B -10, 10% by mass (Nippon Yushi Co., Ltd.) 0.05 parts by mass (as organic peroxide, 0.005 parts by mass), and calcium stearate (trade name: Calcium stearate S, 0.05 parts by mass of Nippon Oil & Fats Co., Ltd.) and tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] me as an antioxidant (Trade name: Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.01 parts by mass, and the mixture was mixed with a tumbler mixer. Using an extruder (manufactured by Tanabe Plastics Co., Ltd.), melt-kneading was performed under the conditions of a cylinder setting temperature of 200 ° C. in the melt-kneading part, a screw rotation speed of 100 rpm, and an extrusion rate: 16 kg / hour. After being filtered through a mesh), it was extruded from a 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 blending amount of each component of the obtained polypropylene resin composition.

(1-2) Manufacture of a polypropylene-based resin composition For evaluation of physical properties by injection molding using pellets made of the polypropylene-based resin composition manufactured by the method (1-1) according to the method for manufacturing an injection-molded body. The test piece was prepared, the physical properties of the test piece were measured after adjusting the predetermined state. The evaluation results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was performed except that the amount of (D-1) was changed to 0.2 parts by mass. The evaluation results are shown in Table 1.

Example 3
The same procedure as in Example 1 was performed except that (A-1) was changed to 67 parts by mass and (B-1) was changed to 25 parts by mass. The results are shown in Table 1.

Example 4
The same procedure as in Example 1 was performed except that (B-1) was changed to 13 parts by mass of (B-2). The results are shown in Table 1.

[Comparative Example 1]
(D-1) 0.3 parts by mass of (D-1) 1,3-o-methylbenzylidene 2,4-p-methylbenzylidene sorbitol (trade name: Gerol DH, manufactured by Shin Nippon Rika Co., Ltd .; comparative product ) Performed in the same manner as in Example 1 except that the content was changed to 0.3 parts by mass. The evaluation results are shown in Table 1.

[Comparative Example 2]
0.3 parts by mass of (D-1) (D-3) 3: 2,4-bis-O-benzylidene-D-glucitol (trade name: Gelol DS, manufactured by Shin Nippon Rika Co., Ltd .; comparative product) 0 . Performed in the same manner as in Example 1 except that the content was changed to 3 parts by mass. The evaluation results are shown in Table 1.

[Comparative Example 3]
(D-1) 0.3 parts by mass of (D-4) 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol (Millad 3988, manufactured by Milliken Japan Co., Ltd., apparent bulk specific gravity: 0 .20 g / cc; comparative product) The same procedure as in Example 1 was performed except that the content was changed to 0.3 parts by mass. The evaluation results are shown in Table 1.

[Comparative Example 4]
(D-1) 0.3 parts by mass (D-5) Nucleating agent mainly composed of an aromatic phosphate ester metal salt (ADK STAB NA-21, manufactured by ADEKA Corporation; comparative product) 0.2 mass The procedure was the same as in Example 1, except that the part was changed. The evaluation results are shown in Table 1.

[Comparative Example 5]
(D-1) Operations were performed in the same manner as in Example 1 except that 0.3 parts by mass was changed to 0.1 parts by mass. The evaluation results are shown in Table 2.

[Comparative Example 6]
(D-1) Operations were performed in the same manner as in Example 1 except that 0.3 parts by mass was changed to 0.6 parts by mass. The evaluation results are shown in Table 2.

[Comparative Example 7]
The same procedure as in Example 1 was performed except that (A-1) was changed to 87 parts by mass and (B-1) was changed to 5 parts by mass. The evaluation results are shown in Table 2.

[Comparative Example 8]
The same procedure as in Example 1 was performed except that (B-1) was changed to 13 parts by mass of (B-3). The evaluation results are shown in Table 2.

[Comparative Example 9]
(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 mass, (D-1) Was carried out in the same manner as in Example 1 except that was changed to 0.3 parts by mass. The evaluation results are shown in Table 2.

[Comparative Example 10]
(C-1) was changed to (C-3) Exelen VL100 (Sumitomo Chemical Co., Ltd., MFR (190 ° C.) = 0.8 g / 10 min, density = 0.900 g / cm ³ ; comparative product) 8 mass%. Was performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Comparative Example 11]
(A-1) is changed to (A-2) 100 parts by mass, (B-1) and (C-1) are not added, and the amount of (E-1) is changed to 0.35 parts by mass. The procedure was the same as in Example 1 except that. The evaluation results are shown in Table 2.

[Comparative Example 12]
(A-1) is changed to (A-2) 96 parts by mass, (B-1) is not blended, (C-1) is replaced with (C-4) Engage 8200 (ethylene-octene copolymer, Dow) Made by Chemical Co., Ltd., MFR (190 ° C.) = 5.0 g / 10 min, density = 0.870 g / cm ³ ; comparative product) In 4 parts by mass, the blending amount of (E-1) is 0.37 mass The procedure was the same as in Example 1 except that the change was made to the part. The evaluation results are shown in Table 2.

[Comparative Example 13]
(A-1) is changed to (A-2) 81 parts by mass, the blending amount of (B-1) is changed to 15 parts by mass, (C-1) is changed to (C-4) engagement 8200 (ethylene- Octene copolymer, manufactured by Dow Chemical Co., Ltd., MFR (190 ° C.) = 5.0 g / 10 min, density = 0.870 g / cm ³ ; comparative product) 4 parts by mass of (E-1) It carried out like Example 1 except having changed the quantity into 0.33 mass part. 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 mass, the following propylene homopolymer (component (B)) 7 to 30% by mass, and the following ethylene copolymer (component (C)) ) A resin mixture containing 2 to 20% by mass (the total of component (A), component (B) and component (C) is 100% by mass), and 100 parts by mass of the resin mixture,
A polypropylene resin composition comprising 0.12 to 0.5 parts by mass of at least one compound (D) represented by the following general formula.

[Wherein n is 0, 1 or 2; A is a non-hydrogen group; and R _{1 to} R ₁₀ are independently of each other hydrogen, fluorocarbon, alkyl group, alkynyl group, alkenyl group, alkoxy group. Selected from the group consisting of a group, a carboxy group, a halogen group, and a phenyl group, and any two adjacent groups may be combined to form a cyclic group.
Ingredient (A):
The content of structural units derived from ethylene is 2 to 5% by mass,
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 Mass%).
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 0.88 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.   The polypropylene resin composition according to claim 1, further comprising an organic peroxide (E) and having a melt flow rate (MFR) measured at 230 ° C of 10 to 100 g / 10 min. .   A molded product comprising the polypropylene resin composition according to claim 1.   A food-filled container or a food packaging molded article comprising the polypropylene-based resin composition according to any one of claims 1 to 3.

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