Composition and molded article containing biomass-derived polypropylene

Abstract

To provide a polypropylene resin composition with a reduced environmental load and excellent impact resistance.SOLUTION: A polypropylene resin composition contains a biomass-derived polypropylene resin B-PP and a petroleum-derived polypropylene resin P-PP. The content of the P-PP is 60-99 pts.wt. based on 100 pts.wt. of the total content of the B-PP and the P-PP. The P-PP contains a polypropylene resin containing a continuous phase comprising a propylene polymer and a dispersed phase comprising a copolymer of ethylene and a C3-10 α olefin. The composition has specific physical properties.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition and a molded article containing biomass-derived polypropylene. [Background technology]

[0002] Biomass materials are being studied to reduce environmental impact. For example, Patent Document 1 discloses a composite material made from biomass raw materials such as starch and wood flour and petroleum-derived polypropylene (Petroleum-based PP, hereinafter also referred to as "P-PP"). A known biomass raw material is biomass-derived polypropylene (biomass-based PP, hereinafter also referred to as "B-PP"), which is obtained by polymerizing propylene obtained from edible oils and other sources. Examples of B-PP on the market include Lyondelbasell's Circulen Renew. B-PP has the same fluidity and mechanical strength as P-PP and does not have odor problems. However, due to factors such as the high raw material cost, B-PP has not been fully utilized. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-059676 Summary of the Invention [Problem to be solved by the invention]

[0004] The inventors conceived the idea of ​​blending P-PP and B-PP and thinning the walls of molded articles to simultaneously reduce CO2 emissions and costs per molded article. However, the inventors discovered that using current P-PP results in reduced impact resistance, making thinning difficult, and also reducing transparency. In light of these circumstances, an objective of the present invention is to provide a polypropylene resin composition that reduces the environmental impact and has excellent impact resistance and transparency. [Means for solving the problem]

[0005] The inventors have solved the above problem by using an optimal P-PP. Aspect 1 A polypropylene resin composition comprising a biomass-derived polypropylene resin B-PP and a petroleum-derived polypropylene resin P-PP, The composition contains 60 to 99 parts by weight of P-PP based on 100 parts by weight of the total of the B-PP and the P-PP, The P-PP is selected from the group consisting of the following compositions (I), (II), and combinations thereof: (I): a propylene copolymer (A1) containing 15% by weight or less of ethylene or one or more C4 to C10 α-olefins; A polypropylene-based resin (A) containing an ethylene copolymer (A2) containing 16 to 25% by weight of one or more C4 to C10 α-olefins as comonomers. Including, the weight ratio of component (A1):component (A2) is 75 to 84% by weight:16 to 25% by weight, The MFR of (A) measured at 230°C and 2.16 kg is less than 2.5 g / 10 min, A composition having an intrinsic viscosity of the total fraction soluble in xylene at room temperature of 1.5 dL / g or less. (II): A polypropylene resin (a) containing an ethylene-propylene copolymer or homopolypropylene (a1) having 1.2% by weight or less of ethylene units and an ethylene-1-butene copolymer (a2) having 16 to 25% by weight of 1-butene units. Including, the xylene-soluble component in (a) has an intrinsic viscosity in tetrahydronaphthalene at 135°C of 0.9 to 1.3 dL / g; The MFR of the (a) measured in accordance with JIS K 7210 at a temperature of 230°C and a weight of 2.16 kg is 30 to 70 g / 10 min, a composition in which the content of the ethylene-1-butene copolymer (a2) is 18 to 30% by weight when the content of the copolymer (a) is taken as 100% by weight; The polypropylene resin composition is Aspect 2 The composition (I) further comprises a nucleating agent (C), The content of the nucleating agent (C) is 0.02 to 0.5 parts by weight per 100 parts by weight of the (A), or The composition (II) further comprises a nucleating agent (C), The content of the nucleating agent (C) is 0.02 to 0.5 parts by weight per 100 parts by weight of the (a). 2. The polypropylene resin composition according to claim 1. Aspect 3 2. The polypropylene resin composition according to embodiment 1, wherein the nucleating agent (C) is a phosphate ester nucleating agent. Aspect 4 The method comprises a step of producing (A) through a sequential polymerization step of polymerizing a corresponding monomer to obtain (A1), and then polymerizing a corresponding monomer in the presence of (A1) to obtain (A2), or With regard to (a), the method includes a step of producing the (a1) by polymerizing a corresponding monomer to obtain the (a2) through a sequential polymerization step of polymerizing a corresponding monomer in the presence of the (a1). A method for producing the polypropylene resin composition according to any one of aspects 1 to 3. Aspect 5 A sheet molded article obtained by molding the polypropylene resin composition according to any one of Aspects 1 to 3, which comprises (I) above. Aspect 6 6. The sheet molded article according to claim 5, having a thickness of 0.35 mm or less. Aspect 7 7. The sheet molded article according to embodiment 5 or 6, which is for use in a container. Aspect 8 An injection-molded article obtained by molding the polypropylene resin composition according to any one of Aspects 1 to 3, which comprises (II) above. Aspect 9 9. The injection-molded article according to embodiment 8, wherein the thickness of the thinnest part is 1 mm or less. Aspect 10 10. The injection-molded article according to aspect 8 or 9, which is molded into the shape of a container, the container having a side wall with a thickness of 0.1 to 1 mm. Aspect 11 11. The injection-molded article according to aspect 10, wherein the thickness of the side wall of the container is 0.1 to 0.45 mm. Aspect 12 When the dart impact strength at 0°C is I (J) and the thickness of the thinnest part of the sheet molding is t (mm), I / t≧4 8. The sheet molded article according to any one of aspects 5 to 7, wherein: [Effects of the Invention]

[0006] The present invention can provide a polypropylene resin composition that reduces the environmental load and has excellent impact resistance. [Brief explanation of the drawings]

[0007] [Figure 1] Diagram explaining the test method for drink container flange strength F50 DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described below. In the present invention, "X to Y" include the extreme values. 1. Polypropylene resin composition The polypropylene resin composition of the present invention comprises a biomass-derived polypropylene resin B-PP and a petroleum-derived polypropylene resin P-PP, and contains 60 to 99 parts by weight of P-PP per 100 parts by weight of the total of B-PP and P-PP, and the P-PP is selected from the group consisting of compositions (I), (II), and combinations thereof.

[0009] [B-PP] Biomass-derived polypropylene resin B-PP is polypropylene derived primarily from plant-derived raw materials. Biomass raw materials are not limited, and examples include edible oil, wood, and paper. The method for producing polypropylene from biomass raw materials is also not limited, and examples include a method in which propylene monomer is extracted from edible oil and then polymerized. A known commercially available product is Circulen Renew from Lyondelbasell. The P-PP content is 60 to 99 parts by weight, based on a total of 100 parts by weight of B-PP and P-PP. From the perspective of reducing environmental impact and achieving a balance between physical properties, the lower limit of the P-PP content is preferably 70 parts by weight or more, and the upper limit is preferably 90 parts by weight or less.

[0010] Depending on the P-PP used, the polypropylene resin composition is roughly divided into a first embodiment suitable for extrusion molding and a second embodiment suitable for injection molding. Each embodiment will be described below.

[0011] [First aspect] In this embodiment, composition (I) is used as P-PP. Composition (I) includes a polypropylene-based resin (A) containing the following: Propylene copolymer (A1): a propylene copolymer containing 15% by weight or less of ethylene or one or more C4 to C10 α-olefins, and Ethylene copolymer (A2): A copolymer containing 16 to 25% by weight of one or more C4 to C10 α-olefins as comonomers. The weight ratio of component (A1):component (A2) is 75 to 84% by weight:16 to 25% by weight.

[0012] (1) Propylene copolymer (A1) The propylene copolymer (A1) (hereinafter also referred to as "component (A1)") contains units derived from a comonomer selected from the group consisting of ethylene, C4-C10 α-olefins, and combinations thereof. The amount of the comonomer-derived units is 15% by weight or less, preferably 10% by weight or less, more preferably 6% by weight or less, even more preferably 2.5 to 5% by weight, and particularly preferably 2.5 to 3.5% by weight, based on the weight of component (A1). If this amount exceeds the upper limit, rigidity decreases. On the other hand, if this amount is too small, transparency deteriorates.

[0013] The C4-C10 α-olefin comonomer can be represented by CH2=CHR. In this formula, R is a linear or branched alkyl group having 2 to 8 carbon atoms, or an aryl group. The aryl group is preferably a phenyl group. More specific examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Among these, from the viewpoints of availability and transparency, the α-olefin is preferably 1-butene.

[0014] (2) Ethylene copolymer (A2) Ethylene copolymer (A2) (hereinafter also referred to as "component (A2)") is an ethylene copolymer containing one or more C4 to C10 α-olefins as comonomers. The α-olefins that can be used are those described for component (A1). The amount of units derived from the comonomer is 16 to 25% by weight, preferably 16 to 24% by weight, based on the weight of component (A2). If this amount is less than the lower limit, impact resistance decreases, and if this amount is too large, rigidity decreases.

[0015] (3) Characteristics of polypropylene resin (A) The polypropylene resin (A) (hereinafter also referred to as "component (A)") has the following properties: 1) Weight ratio The weight ratio of component (A1):component (A2) is 75-84% by weight:16-25% by weight, and preferably 77-83% by weight:17-23% by weight.

[0016] 2) MFR The MFR of component (A), measured at 230°C and 2.16 kg, is less than 2.5 g / 10 min, preferably 1.5 to 2.0 g / 10 min. If the MFR exceeds the upper limit, impact resistance decreases. If the MFR is below the lower limit, productivity decreases.

[0017] 3)XSIV The intrinsic viscosity (hereinafter also referred to as "XSIV") of the total fraction soluble in xylene at room temperature is 1.5 dL / g or less, preferably 0.9 to 1.5, and more preferably 0.95 to 1.5 dL / g. If the viscosity exceeds the upper limit, productivity decreases. If the viscosity is below the lower limit, impact resistance decreases. The xylene-soluble component is a component obtained by dissolving a polypropylene resin sample in o-xylene at 135°C, cooling it to 25°C, filtering the cooled solution using filter paper, and evaporating the filtrate to dryness.

[0018] (3) Nucleating agent (C) Composition (I) may contain a nucleating agent (C). Nucleating agents are also called crystal nucleating agents. As the nucleating agent (C), known nucleating agents used in conventional polypropylene-based resin compositions can be used, and it is preferably selected from nonitol-based nucleating agents, sorbitol-based nucleating agents, phosphate ester-based nucleating agents, triaminobenzene derivative nucleating agents, metal carboxylate nucleating agents, and xylitol-based nucleating agents. Talc can also be used as a nucleating agent. From the viewpoint of reducing the odor of injection-molded articles, phosphate ester-based nucleating agents are preferred.

[0019] Examples of nucleating agents having a nonitol-based structure include 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonitol; examples of nucleating agents having a xylitol-based structure include bis-1,3:2,4-(5',6',7',8'-tetrahydro-2-naphthaldehyde benzylidene)1-allylxylitol and bis-1,3:2,4-(3',4'-dimethylbenzylidene)1-propylxylitol; and examples of nucleating agents having a sorbitol-based structure include bis-1,3:2,4-(4'-ethylbenzylidene)1-allylsorbitol, bis-1,3:2,4-(3'-methyl-4'-fluoro-benzylidene)1-propylsorbitol and bis-1,3:2,4-(3',4'-dimethylbenzylidene). 2'-methyl-2'-propenyl sorbitol, bis-1,3,2,4-dibenzylidene 2',3'-dibromopropyl sorbitol, bis-1,3,2,4-dibenzylidene 2'-bromo-3'-hydroxypropyl sorbitol, 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-methyl sorbitol, bis(p-methylbenzylidene)sorbitol, 1,3:2,4-bis-o-(4-methylbenzylidene)-D-sorbitol, and the like.

[0020] Examples of commercially available nonitol-based nucleating agents include Millad NX8000 (manufactured by Milliken Japan Co., Ltd.), and examples of commercially available sorbitol-based nucleating agents include RiKAFAST R-1 (manufactured by New Japan Chemical Co., Ltd.), Millad 3988 (manufactured by New Japan Chemical Co., Ltd.), Gelall E-200 (manufactured by New Japan Chemical Co., Ltd.), and Gelall MD (manufactured by New Japan Chemical Co., Ltd.).

[0021] Examples of phosphate ester-based crystal nucleating agents include sodium 2,2-methylenebis(4,6-di-tert-butylphenyl)phosphate, aluminum 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, and lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate. Examples of commercially available phosphate ester-based crystal nucleating agents include Adeka STAB NA-11 (manufactured by ADEKA Corporation), Adeka STAB NA-21 (manufactured by ADEKA Corporation), and Adeka STAB NA-71 (manufactured by ADEKA Corporation).

[0022] Examples of triaminobenzene derivative crystal nucleating agents include 1,3,5-tris(2,2-dimethylpropanamido)benzene, etc. Examples of commercially available triaminobenzene derivative crystal nucleating agents include IRGACLEAR XT386 (manufactured by BASF Japan Ltd.) and RIGACLEAR PC1 (manufactured by New Japan Chemical Co., Ltd.).

[0023] Examples of metal carboxylate nucleating agents include calcium 1,2-cyclohexanedicarboxylate. Examples of commercially available metal carboxylate nucleating agents include Hyperform HPN-20E (manufactured by Milliken Japan Co., Ltd.). These crystal nucleating agents can be used alone or in combination of two or more.

[0024] When a nucleating agent (C) is used, its content is preferably 0.02 to 0.5 parts by weight per 100 parts by weight of component (A). If the content is equal to or greater than the lower limit, the rigidity of the molded article increases. On the other hand, if the content exceeds the upper limit, the effect of improving the rigidity of the molded article reaches a plateau, making it uneconomical.

[0025] (4) Method for producing composition (I) Composition (I) is preferably produced by mixing component (A) and, if necessary, nucleating agent (C) together, followed by melt-kneading. Examples of mixing methods include dry blending using a mixer such as a Henschel mixer, a tumbler, or a ribbon mixer. Examples of melt-kneading methods include mixing while melting using a mixer such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, or a roll mill. The melting temperature during melt-kneading is preferably 160 to 350°C, more preferably 170 to 260°C. After melt-kneading, the mixture may be further pelletized.

[0026] The composition (I) is preferably produced through a sequential polymerization step in which a corresponding monomer of the (A) is polymerized to obtain the (A1) and then a corresponding monomer is polymerized in the presence of the (A1) to obtain the (A2).

[0027] A multistage polymerization method is typically used to produce the polymerization mixture. For example, in a polymerization apparatus equipped with two polymerization reactors, propylene monomer and, if necessary, ethylene monomer are polymerized in the first polymerization reactor to obtain a propylene polymer, and the resulting propylene polymer is supplied to the second polymerization reactor, while the ethylene monomer and propylene monomer are polymerized in the second polymerization reactor, thereby obtaining the polymerization mixture. The polymerization conditions may be similar to known polymerization conditions. For example, the first-stage polymerization conditions include slurry polymerization, in which propylene is in a liquid phase and provides high monomer density and productivity. The second-stage polymerization conditions include gas-phase polymerization, which generally facilitates the production of copolymers highly soluble in propylene. The polymerization temperature is preferably 50 to 90°C, more preferably 60 to 90°C, and even more preferably 70 to 90°C. A polymerization temperature equal to or higher than the lower limit of the above range results in superior productivity and the resulting polypropylene having superior stereoregularity.

[0028] The polymerization pressure is preferably 25 to 60 bar (2.5 to 6.0 MPa) when carried out in a liquid phase, and more preferably 33 to 45 bar (3.3 to 4.5 MPa). When carried out in a gas phase, it is preferably 5 to 30 bar (0.5 to 3.0 MPa), and more preferably 8 to 30 bar (0.8 to 3.0 MPa). Polymerization is usually carried out using a catalyst. During polymerization, hydrogen may be added, if necessary, to adjust the molecular weight. The MFR of the polypropylene resin (A) and, therefore, the MFR of the composition (I) can be adjusted by adjusting the molecular weight of the propylene polymer or ethylene-propylene copolymer. Prior to polymerization in the first-stage polymerization reactor, propylene may be prepolymerized to form polymer chains on the solid catalyst component, which will serve as a foothold for the subsequent main polymerization. Prepolymerization is usually carried out at 40°C or below, preferably 30°C or below, and more preferably 20°C or below.

[0029] As the catalyst, a known olefin polymerization catalyst can be used. As the catalyst, a stereospecific Ziegler-Natta catalyst is preferred, and a catalyst containing the following components (x), (y), and (z) (hereinafter also referred to as "catalyst (X)") is particularly preferred. (x) A solid catalyst containing magnesium, titanium, a halogen, and an electron donor compound as essential components. (y) Organoaluminum compounds. (z) Organosilicon compounds that are external electron donor compounds

[0030] Component (x) is prepared using, for example, a titanium compound, a magnesium compound, and an electron donor compound. The titanium compound used in component (x) is a compound represented by the general formula: Ti(OR) g X 4-g (R is a hydrocarbon group, X is a halogen, 0≦g≦4) is preferred. Examples of the hydrocarbon group include methyl, ethyl, propyl, and butyl, and examples of the halogen include Cl and Br. More specific examples of titanium compounds that can be used include titanium tetrahalides such as TiCl4, TiBr4, and TiI4, as well as those disclosed in JP 2021-176923 A.

[0031] Examples of the magnesium compound used in component (x) include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butylethoxy magnesium, ethylbutyl magnesium, butyl magnesium hydride, etc. More specifically, those disclosed in JP 2021-176923 A can be used.

[0032] The electron donor compound used in component (x) may be a phthalate compound. Examples of the phthalate compound include monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, mono-n-butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl-n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, and diphenyl phthalate. Among these, diisobutyl phthalate is particularly preferred.

[0033] Examples of the electron donor compound in the solid catalyst other than the phthalate compound include esters of mono- or dicarboxylic acids or diether compounds. Examples of the mono- or dicarboxylic acid esters include benzoates, malonates, phthalates, or succinates. Specific examples of these compounds include those disclosed in JP 2021-176923 A.

[0034] The halogen atoms constituting component (x) include fluorine, chlorine, bromine, iodine, or mixtures thereof, with chlorine being preferred.

[0035] As the organoaluminum compound of component (y), for example, trialkylaluminum such as triethylaluminum and tributylaluminum, as well as those disclosed in JP-A-2021-176923 can be used.

[0036] The external electron donor compound of component (z) is an organosilicon compound. Preferred organosilicon compounds include, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, and bis-p-tolyldimethoxysilane. Ethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, biphenyltrimethoxysilane, Nyltriethoxysilane, t-butyltriethoxysilane, thexyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ketone Ethyl methyl acrylate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, cyclohexylethyldimethoxysilane, cyclopentyl-t-butoxydimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyldimethoxysilane, n-propyltrimethoxysilane, di-n-propyldimethoxysilane,t-Butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butyl-t-butoxydimethoxysilane, isobutyltrimethoxysilane, cyclohexylisobutyldimethoxysilane, di-sec-butyldimethoxysilane, isobutylmethyldimethoxysilane, bis(decahydroisoquinolin-2-yl)dimethoxysilane, diethylaminotriethoxysilane, dicyclopentyl-bis(ethylamino)silane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane Examples of suitable silanes include dimethylsilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl(perhydroisoquinolin-2-yl)dimethoxysilane, tri(isopropenyloxy)phenylsilane, i-butyl-i-propyldimethoxysilane, cyclohexyl-i-butyldimethoxysilane, cyclopentyl-i-butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, phenyltriethoxysilane, and p-tolylmethyldimethoxysilane. Among these, ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl(perhydroisoquinolin-2-yl)dimethoxysilane, bis(decahydroisoquinoline- 2-yl)dimethoxysilane, tri(isopropenyloxy)phenylsilane, thexyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyli-propyldimethoxysilane, cyclopentylt-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyli-butyldimethoxysilane, cyclopentyli-butyldimethoxysilane,Preferred examples include cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, and ethyl silicate. One of these may be used alone, or two or more may be used in combination.

[0037] The organosilicon compound plays an important role in controlling the amount of xylene insolubles. When other catalyst components are the same, the amount of xylene insolubles depends on the type and amount of organosilicon compound and the polymerization temperature. Even when an appropriate organosilicon compound is used, the amount of organosilicon compound drops significantly when the amount of organosilicon compound falls below a certain value, except for diether catalysts. Therefore, when the polymerization temperature is 75°C, the lower limit of the molar ratio of organosilicon compound to organoaluminum compound (organosilicon compound / organoaluminum) is preferably 0.015, more preferably 0.018. The upper limit of this ratio is preferably 0.30, more preferably 0.20, and even more preferably 0.10.

[0038] When a phthalate-based compound is used as the internal electron donor compound, increasing the polymerization temperature increases the amount of xylene-insoluble matter, thereby lowering the upper and lower limits of the preferred molar ratio of the organosilicon compound to the organoaluminum compound (organosilicon compound / organoaluminum). Specifically, when polymerizing at 80°C using a phthalate-based compound, the lower limit of the molar ratio is preferably 0.010, more preferably 0.015, and even more preferably 0.018. The upper limit of the molar ratio is preferably 0.20, more preferably 0.14, and even more preferably 0.08.

[0039] As the catalyst (X), a catalyst in which the component (y) is a trialkylaluminum such as triethylaluminum or triisobutylaluminum, and the component (z) is an organosilicon compound such as dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane or diisopropyldimethoxysilane is preferred.

[0040] The method for obtaining the polymerization mixture by multistage polymerization is not limited to the above method. Component (A1) may be polymerized in multiple polymerization reactors, or component (A2) may be polymerized in multiple polymerization reactors. Methods for obtaining the polymerization mixture include a method using a polymerization reactor with a gradient of monomer concentration or polymerization conditions. Such a polymerization reactor, for example, may be one in which at least two polymerization zones are joined together, and the monomers can be polymerized by gas-phase polymerization. Specifically, in the presence of a catalyst, monomers are supplied and polymerized in a polymerization zone consisting of a riser pipe, and then monomers are supplied and polymerized in a downcomer pipe connected to the riser pipe. The polymerization product is recovered while circulating between the riser pipe and the downcomer pipe. This method includes a means for completely or partially preventing the gas mixture present in the riser pipe from entering the downcomer pipe. Furthermore, a gas or liquid mixture having a different composition from the gas mixture present in the riser pipe is introduced into the downcomer pipe. For example, the polymerization method described in JP-A-2002-520426 can be applied to this polymerization method.

[0041] (5) Other ingredients The polypropylene resin composition according to the first aspect, which contains B-PP and composition (I), may optionally contain additives other than those described above, provided that the effects of the present invention are not impaired. Examples of such additives include antioxidants, neutralizing agents, nucleating agents other than those described above, weathering agents, pigments (organic or inorganic), internal and external lubricants, antiblocking agents, antistatic agents, chlorine absorbers, heat stabilizers, light stabilizers, UV absorbers, slip agents, antifogging agents, flame retardants, dispersants, copper inhibitors, plasticizers, foaming agents, anti-foaming agents, crosslinking agents, peroxides, and oil extenders. These additives may be used alone or in combination of two or more. The content of these additives may be in known amounts.

[0042] (6) Sheet molding The polypropylene resin composition of this embodiment is suitable for extrusion molding, particularly sheet molding. The sheet can be produced by, for example, a cast molding method. The molding temperature is, for example, 150 to 350°C, preferably 170 to 250°C. The sheet can be further processed into secondary products such as containers, and the sheet of this embodiment is particularly useful for food products.

[0043] The thickness of the sheet molded body is preferably more than 0.1 mm and 0.5 mm or less. The upper limit is adjusted appropriately depending on the application, but can be 0.4 mm or less, 0.35 mm or less, 2.0 mm or less, or 1.0 mm or less. The thickness of the sheet molded body is measured by a known method such as a beta ray thickness meter.

[0044] The sheet molded article has excellent transparency. Furthermore, since the sheet molded article has excellent impact resistance at extremely low temperatures, it can be used in low-temperature environments, for example, at temperatures of -50°C to 0°C, preferably -45°C to -10°C, and more preferably -40°C to -20°C. The dart impact strength (also called high-rate impact) (unit: J) of the sheet molded article at 0°C is preferably 2 or more, with higher values ​​being more preferable. The dart impact strength is measured in accordance with JIS K7211-2 using a puncture impact tester (Hydroshot HITS-P10 manufactured by Shimadzu Corporation). The higher the dart impact strength, the better the impact resistance.

[0045] The sheet molding preferably satisfies the following relationship, where I (J) is the dart impact strength at 0° C. and t (mm) is the thickness of the thinnest part of the sheet molding. I / t≧4

[0046] I / t is the ratio of surface impact strength to thickness, and the higher this value, the thinner the sheet molding is and the better its impact resistance. A thinner molding means less carbon dioxide emissions per molding, making it a material with a lower environmental impact.

[0047] [Second aspect] In this embodiment, composition (II) is used as P-PP. Composition (II) includes a polypropylene-based resin (a) containing the following: Propylene (co)polymer (a1): ethylene-propylene copolymer or homopolypropylene having an ethylene unit content of 1.2% by weight or less, and Ethylene-1-butene copolymer (a2): A copolymer containing 16 to 25% by weight of 1-butene units.

[0048] (1) Propylene (co)polymer (a1) The propylene (co)polymer (a1) (hereinafter also referred to as "component (a1)") is a homopolypropylene or an ethylene-propylene copolymer containing 1.2% by weight or less of ethylene units. The ethylene units refer to units derived from ethylene. The same applies to other units. The ethylene unit content is preferably 0 to 0.6% by weight based on the weight of component (a1). If the ethylene unit content exceeds the upper limit, the rigidity and thin-wall moldability of composition (II) may decrease.

[0049] (2) Ethylene-1-butene copolymer (a2) The 1-butene unit content in the ethylene-1-butene copolymer (a2) (hereinafter also referred to as "component (a2)") is 16 to 25% by weight, based on the weight of component (a2). The 1-butene unit content is preferably 16 to 20% by weight. If the content exceeds the upper limit, the low-temperature impact strength of composition (II) tends to decrease. If the content is below the lower limit, production of the polypropylene-based resin tends to become difficult, and the rigidity, transparency, and thin-wall moldability of composition (II) may decrease.

[0050] The content of the ethylene-1-butene copolymer in the polypropylene-based resin (a) (hereinafter also referred to as component (a)) is 18 to 30% by weight, preferably 19 to 29% by weight, and more preferably 20 to 28% by weight, based on 100% by weight of component (a). If the content exceeds the upper limit, the productivity of the polypropylene-based resin tends to decrease, while if it is less than the lower limit, the low-temperature impact resistance of the composition (II) tends to decrease.

[0051] (3) Characteristics of polypropylene resin (a) 1)XSIV The xylene-soluble portion of component (a) has an intrinsic viscosity (XSIV) in tetrahydronaphthalene at 135°C of 0.9 to 1.3 dL / g, preferably 0.95 to 1.15 dL / g. If the XSIV exceeds the upper limit, the whitening resistance and transparency tend to decrease. If the XSIV is less than the lower limit, the productivity of polypropylene-based resin (a) decreases.

[0052] 2) MFR The MFR of component (a), measured at 230°C and 2.16 kg in accordance with JIS K 7210, is 30 to 70 g / 10 min, and preferably 40 to 60 g / 10 min. The MFR is measured in accordance with JIS K 7210. If the MFR is less than the lower limit, thin-wall formability will be poor, and if it exceeds the upper limit, low-temperature impact resistance will be poor.

[0053] 3) Molecular weight The weight average molecular weight of component (a) is preferably 160,000 to 210,000. If the molecular weight is within this range, the MFR of component (a) can be easily adjusted to 30 to 70 g / 10 min.

[0054] (3) Nucleating agent (C) Composition (II) may contain the aforementioned nucleating agent (C). The amount thereof is 0.02 to 0.5 parts by weight per 100 parts by weight of component (a). The preferred amount and type of nucleating agent are as described in the first embodiment.

[0055] (4) Method for producing composition (II) The method for producing the composition (II) includes a method of mixing the polypropylene resin (a) and, if necessary, the nucleating agent (C) and then melt-kneading the mixture. Examples of the mixing method include dry blending using a mixer such as a Henschel mixer, a tumbler, or a ribbon mixer. Examples of the melt-kneading method include mixing while melting using a mixer such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, or a roll mill. The melting temperature during melt-kneading is preferably 160 to 350°C, more preferably 170 to 260°C. After melt-kneading, the mixture may be further pelletized.

[0056] Component (a) is produced in the same manner as component (A) described in the first embodiment. The catalyst used is also as described in the first embodiment.

[0057] (5) Other ingredients The polypropylene resin composition according to the second aspect, which contains B-PP and composition (II), may optionally contain additives other than the above-mentioned components, provided that the additives do not impair the effects of the present invention. The additives are as described in the first aspect.

[0058] (6) Injection molding The polypropylene resin composition according to this embodiment is suitable for injection molding. The molding temperature is generally 150 to 350°C, preferably 170 to 250°C. A molding temperature exceeding 350°C may cause deterioration of the resin composition and molding defects, while a temperature lower than 150°C may result in poor fluidity, leading to insufficient filling of the mold, resulting in poor appearance and molding defects.

[0059] The mold temperature is preferably 10 to 60°C. If the mold temperature exceeds 60°C, the molded product will have an excellent surface finish and excellent rigidity, but the molding cycle will be longer and productivity will decrease. Conversely, if the mold temperature is set lower than 10°C, warping and shrinkage will become more pronounced, making it difficult to obtain satisfactory molded products. In addition, condensation will easily form on the mold, which will accelerate mold corrosion and is undesirable from the standpoint of energy costs related to cooling.

[0060] The polypropylene resin composition according to this embodiment is suitable for thin-wall injection molding. For example, it is possible to form an injection-molded article having a thickness of 1 mm or less at the thinnest part, preferably 0.7 mm or less, and more preferably 0.45 mm or less. The lower limit of the thickness of the thin-walled part is approximately 0.1 mm. The thickness of the thin-walled part is measured by observing the cross section of the measurement point using a known means such as a measuring microscope.

[0061] The shape of the injection-molded article is not particularly limited, and it is suitable for containers because it has an excellent balance of various mechanical properties and can be made thin. The thickness of the side wall of the container can be, for example, 0.1 to 1 mm, preferably 0.1 to 0.7 mm, and more preferably 0.1 to 0.45 mm. The thickness of the side wall is measured by observing the cross section of the measurement point using a known means such as a measuring microscope.

[0062] When the injection-molded article is a container, an in-mold label may be provided on the side wall of the container. An in-mold label may wrap around the side wall (one full circle) and have a joint where the starting edge and the ending edge overlap. Typically, the main body of the in-mold label is formed of a resin different from the polypropylene-based resin composition that forms the container body. The thickness of the in-mold label may be, for example, 10 to 100 μm. The thickness of the in-mold label is included in the thickness of the side wall of the container. The in-mold label may be printed with letters, pictures, symbols, numbers, or any other figures or designs.

[0063] The injection molded article has excellent low-temperature impact resistance, and can be used in low-temperature environments, for example, at -10°C or below, preferably -20°C or below, and more preferably -30°C or below.

[0064] The injection-molded article of the present invention is formed from a polypropylene-based resin composition that is excellent in transparency and food hygiene, and is therefore suitable for use as a container or packaging material that comes into contact with food.

[0065] The properties of the polymer are preferably measured as follows: Although the following examples are given for components (a1) and (a2), the same applies to components (A1) and (A2). [Mw / Mn of component (a1)] The polymerized component (a1) is analyzed by GPC. 1,2,4-trichlorobenzene containing an antioxidant is preferably used as the mobile phase. Column calibration is preferably performed by cubic approximation using polystyrene standards.

[0066] [Total ethylene content of copolymer, content of ethylene-derived units in component (a1)] Sample 13 A C-NMR spectrum is obtained, and the total ethylene content (wt%) of the copolymer sample is determined by the method described in Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules, 15, 1150-1152 (1982).

[0067] [Content of ethylene-derived units in component (a2)] The ethylene-derived unit content (wt%) of component (a2) is determined by the same method as for the total ethylene content, except that the integrated intensity T'ββ calculated by the following formula is used instead of the integrated intensity Tββ calculated when measuring the total ethylene content of the copolymer by the method described in the above document. T'ββ=0.98×Sαγ×A / (1-0.98×A) Here, A=Sαγ / (Sαγ+Sαδ), and is calculated from Sαγ and Sαδ described in the above-mentioned document. In a copolymer consisting of components (a1) and (a2), when component (a1) contains ethylene units, the content of ethylene-derived units in component (a2) can be calculated by the following formula, provided that the weight ratio of component (a2) / [component (a1)+component (a2)] is clear from the polymerization conditions. Ethylene-derived unit content of component (a2) (unit: wt%)= [Total ethylene content of copolymer - the content of ethylene-derived units in component (a1) × the content ratio of component (a1) in the copolymer] / (content of component (a2) in copolymer)

[0068] [Component (a1) + component (a2) XSIV] A sample is dissolved in o-xylene, and the xylene-soluble fraction is separated from the resulting solution. The xylene-soluble fraction is dissolved in tetrahydronaphthalene and measured using a capillary viscometer. [Example]

[0069] [Polymer 1] As B-PP, a propylene polymer Circulen HP525J (MFR=2.0 g / 10 min, biomass content=50 wt %) manufactured by Lyondelbasell was used.

[0070] [Synthesis of copolymer 2] A solid catalyst in which Ti and diisobutyl phthalate as an internal donor were supported on MgCl was prepared by the method described in Example 5 of EP 728769. The solid catalyst was then contacted with triethylaluminum (TEAL) as an organoaluminum compound and dicyclopentyldimethoxysilane (DCPMS) as an external electron donor compound at a weight ratio of 20% to the solid catalyst and a weight ratio of 10% to the TEAL / DCPMS, respectively, at 12°C for 24 minutes. The resulting catalyst system was prepolymerized by maintaining the suspension in liquid propylene at 20°C for 5 minutes. The resulting prepolymer was introduced into the first-stage polymerization reactor of a polymerization apparatus equipped with two series reactors. Ethylene was fed into the liquid-phase propylene to produce propylene-ethylene random copolymer (Component (A1)), and ethylene-1-butene copolymer (Component (A2)) was produced in the second-stage gas-phase polymerization reactor. During the polymerization, the temperature and pressure were controlled, and hydrogen was used as a molecular weight regulator.

[0071] The polymerization temperature, hydrogen concentration, and ethylene concentration in the first reactor were 70°C, 0.054 mol%, and 0.80 mol%, respectively, while the polymerization temperature, H2 / C2, and C4 / (C2+C4) were 80°C, 0.30 mol%, and 0.48 mol%, respectively, in the second reactor. The residence time distribution between the first and second stages was adjusted so that the amount of component (A2) was 18 wt%.

[0072] To 100 parts by weight of copolymer 2, 0.04 parts by weight of antioxidant Irganox 1010 (manufactured by BASF), 0.04 parts by weight of processing heat stabilizer Irganophos 168 (manufactured by BASF), and 0.05 parts by weight of calcium stearate (manufactured by Dannan Chemical Industry Co., Ltd.) as a neutralizer were added, and the mixture was stirred and mixed for 1 minute using a Henschel mixer. The mixture was melt-kneaded and extruded at a cylinder temperature of 230°C using a co-rotating twin-screw extruder TEX-30α (manufactured by JSW Corporation). The strand was cooled in water and then cut using a pelletizer to obtain pellets of copolymer 2 composition.

[0073] [Synthesis of copolymer 3] A solid catalyst in which Ti and diisobutyl phthalate as an internal donor were supported on MgCl2 was prepared by the method described in lines 21 to 36 of paragraph 0032 of JP-A 2004-27218. The solid catalyst was used to carry out prepolymerization by suspending it in liquid propylene at 20°C for 5 minutes. The resulting prepolymer was introduced into the first-stage polymerization reactor of a polymerization apparatus equipped with two polymerization reactors connected in series, and propylene was supplied to produce a propylene homopolymer (component (A1)). Subsequently, the propylene homopolymer, propylene, and ethylene were supplied to the second-stage polymerization reactor to produce an ethylene-propylene copolymer (component (A2)). During polymerization, the temperature and pressure were adjusted, and hydrogen was used as a molecular weight modifier. The polymerization temperature and hydrogen concentration of the first-stage reactor were 80°C and 0.139 mol%, respectively. The polymerization temperature, hydrogen concentration, and ratio of ethylene to the total of ethylene and propylene of the second-stage reactor were 80°C, 1.06 mol%, and 0.51 mol ratio, respectively. The residence time distribution in the first and second stages was adjusted so that the weight ratio of component (A2) / [component (A1)+component (A2)] was 21% by weight.

[0074] To 100 parts by weight of copolymer 3, 0.04 parts by weight of antioxidant Irganox 1010 (manufactured by BASF), 0.04 parts by weight of processing heat stabilizer Irganofos 168 (manufactured by BASF), and 0.05 parts by weight of calcium stearate (manufactured by Dannan Chemical Industry Co., Ltd.) as a neutralizer were added, and the mixture was stirred and mixed for 1 minute using a Henschel mixer. The mixture was melt-kneaded and extruded at a cylinder temperature of 230°C using a co-rotating twin-screw extruder TEX-30α (manufactured by JSW Corporation). The strand was cooled in water and then cut using a pelletizer to obtain pellets of copolymer 3 composition.

[0075] [Polymer 4] As B-PP, a propylene polymer Circulen HP483R (MFR=30.0 g / 10 min, biomass content=50 wt %) manufactured by Lyondelbasell was used.

[0076] [Synthesis of copolymer 5] In the first-stage reactor, ethylene was not fed, and the hydrogen concentration was changed to 0.850 mol% to polymerize a propylene homopolymer. In the second-stage reactor, the H2 / C2 and C4 / (C2+C4) molar ratios were changed to 0.30 and 0.39, respectively, and the residence time distributions in the first and second stages were adjusted so that the amount of ethylene-1-butene copolymer was 27 wt%. Copolymer 5 was obtained by the same production method as for Copolymer 2.

[0077] To 100 parts by weight of Copolymer 5, 0.04 parts by weight of the antioxidant Irganox 1010 (manufactured by BASF), 0.04 parts by weight of the processing heat stabilizer Irganofos 168 (manufactured by BASF), and 0.05 parts by weight of calcium stearate (manufactured by Dannan Chemical Industry Co., Ltd.) as a neutralizer were added, and the mixture was stirred and mixed for 1 minute using a Henschel mixer. The mixture was melt-kneaded and extruded at a cylinder temperature of 230°C using a co-rotating twin-screw extruder TEX-30α (manufactured by JSW Corporation). The strand was cooled in water and then cut using a pelletizer to obtain pellets of the Copolymer 5 composition.

[0078] [Synthesis of copolymer 6] The hydrogen concentration in the first reactor was changed to 2.22 mol%, and the hydrogen concentration in the second reactor and the ratio of ethylene to the total of ethylene and propylene were changed to 1.88 mol% and 0.45 mol ratio, respectively, and the residence time distribution in the first and second reactors was adjusted so that the weight ratio of component (a2) / [component (a1) + component (a2)] was 16 wt%. Copolymer 6 was obtained by the same production method as for Copolymer 3.

[0079] To 100 parts by weight of Copolymer 6, 0.04 parts by weight of the antioxidant Irganox 1010 (BASF), 0.04 parts by weight of the heat stabilizer Irganophos 168 (BASF), and 0.05 parts by weight of calcium stearate (manufactured by Dannan Chemical Industry Co., Ltd.) as a neutralizer were added, and the mixture was stirred and mixed for 1 minute using a Henschel mixer. The mixture was melt-kneaded and extruded at a cylinder temperature of 230°C using a co-rotating twin-screw extruder TEX-30α (manufactured by JSW Corporation). The strands were cooled in water and then cut using a pelletizer to obtain pellets of the Copolymer 6 composition. The physical properties of these components are shown in Table 1.

[0080] [Table 1]

[0081] The properties shown in Table 1 were measured as follows. The following describes the components (a1) and (a2), but the same measurements were also taken for the components (A1) and (A2). [Mw / Mn of component (a1)] A 2.5 g sample taken from the component (a1) polymerized in the first-stage reactor was used as a measurement sample, and the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured as follows, and the weight average molecular weight (Mw) was divided by the number average molecular weight (Mn) to determine the molecular weight distribution (Mw / Mn). The Polymer Laboratories PL GPC220 was used as the instrument, and 1,2,4-trichlorobenzene containing an antioxidant was used as the mobile phase. A series of Showa Denko UT-G (1 column), UT-807 (1 column), and UT-806M (2 columns) was used as the column. A differential refractometer was used as the detector. The sample solution was prepared using the same solvent as the mobile phase, with a sample concentration of 1 mg / mL. The sample was dissolved at 150 °C for 2 hours with shaking. 500 μL of the resulting sample solution was injected into the column, and measurements were performed at a flow rate of 1.0 mL / min, a temperature of 145 °C, and a data acquisition interval of 1 second. The column was calibrated using polystyrene standards (Shodex STANDARD, Showa Denko) with molecular weights ranging from 5.8 million to 7.45 million, using a cubic approximation. The Mark-Houwink-Sakurada coefficient for the polystyrene standards was K = 1.21 × 10. -4 , α=0.707, for polypropylene-based polymers, K=1.37×10 -4 , α=0.75 was used.

[0082] [Total ethylene content of copolymer, content of ethylene-derived units in component (a1)] The copolymer sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene was analyzed by a Bruker AVANCEIII HD400 ( 13 C resonance frequency 100MHz) under the conditions of measurement temperature 120℃, flip angle 45 degrees, pulse interval 7 seconds, sample rotation speed 20Hz, and cumulative number 5000. 13 C-NMR spectra were obtained. Using the spectrum obtained above, the total ethylene content (wt%) of the copolymer sample was determined by the method described in Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules, 15, 1150-1152 (1982). When component (a1) is used as a sample for measurement, the total ethylene amount (wt%) obtained by the above method is the ethylene-derived unit content (wt%) of component (a1).

[0083] [Content of ethylene-derived units in component (a2)] The ethylene-derived unit content (wt%) of component (a2) was determined by the same method as for the total ethylene content, except that the integrated intensity T'ββ calculated by the following formula was used instead of the integrated intensity Tββ calculated when measuring the total ethylene content of the copolymer by the method described in the above document. T'ββ=0.98×Sαγ×A / (1-0.98×A) Here, A=Sαγ / (Sαγ+Sαδ), and is calculated from Sαγ and Sαδ described in the above-mentioned document. In a copolymer consisting of components (a1) and (a2), when component (a1) contains ethylene units, the content of ethylene-derived units in component (a2) was calculated by the following formula when the weight ratio of component (a2) / [component (a1)+component (a2)] was clear from the polymerization conditions. Ethylene-derived unit content of component (a2) (unit: wt%)= [Total ethylene content of copolymer - the content of ethylene-derived units in component (a1) × the content ratio of component (a1) in the copolymer] / (content of component (a2) in copolymer)

[0084] <Weight ratio component (a2) / [component (a1) + component (a2)]> It was calculated using the following formula. Component (a2) / [Component (a1)+Component (a2)] (unit: weight %)=Total ethylene content of copolymer / (Content of ethylene-derived units in component (a2) / 100)

[0085] [Component (a1) + component (a2) XSIV] The xylene soluble fraction of the copolymer was obtained by the following method, and the intrinsic viscosity (XSIV) of the xylene soluble fraction was measured. A 2.5 g sample of the copolymer was placed in a flask containing 250 mL of o-xylene (solvent). The mixture was stirred for 30 minutes using a hot plate and reflux hood at 135°C while purging with nitrogen to completely dissolve the copolymer, and then cooled to 25°C for 1 hour. The resulting solution was filtered using filter paper. 100 mL of the filtrate was transferred to an aluminum cup or similar container and evaporated to dryness at 140°C while purging with nitrogen. The mixture was then left to stand at room temperature for 30 minutes to obtain the xylene-soluble fraction. The intrinsic viscosity was measured in tetrahydronaphthalene at 135° C. using an automatic capillary viscosity measuring device (SS-780-H1, manufactured by Shibayama Scientific Instruments Co., Ltd.).

[0086] <MFR of component (a1) + component (a2)> In the examples, 5 g pellets of the composition were measured in accordance with JIS K6921-2 under conditions of a temperature of 230° C. and a load of 2.16 kg.

[0087] [Examples S1 to S5, and Comparative Examples S1 and S2] The components were blended according to the composition shown in Table 2. 0.2 parts by weight of BASF B225 as an antioxidant and 0.05 parts by weight of Dannan Chemical Industry Co., Ltd. calcium stearate as a neutralizer were added to 100 parts by weight of the total amount of B-PP and P-PP, and the mixture was stirred and mixed for 1 minute using a Henschel mixer. The mixture was melt-kneaded and extruded at a cylinder temperature of 230°C using a co-rotating twin-screw extruder TEX-30α manufactured by JSW Corporation. The strands were cooled in water and then cut using a pelletizer to obtain pellets of the polypropylene resin composition. The resulting pellets were used to produce sheet molded articles using the method described below. Various physical properties of the resulting sheet molded articles were evaluated.

[0088] Using a Thermoplastics Industries Co., Ltd., 3-type, 3-layer, φ25mm film / sheet molding machine, the cylinder to die temperature was adjusted to 250°C, and the pellets were used as raw material. The molten resin extruded from the die was cooled and solidified on a cooling roll at a molding speed of 1.0 m / min, and then drawn off to obtain a 400 μm thick sheet. The molded sheet was conditioned in a 23°C thermostatic chamber for at least 48 hours before being used as a sample.

[0089] The following nucleating agents were used: C-1: Clearmaster R8020 manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. (NX8000 manufactured by Milliken (nonitol-based nucleating agent masterbatch)) C-2: ADEKA M801 (ADEKA STAB NA71 (phosphate ester nucleating agent masterbatch))

[0090] [Table 2]

[0091] The evaluation was carried out as follows: [Haze] The haze of the sheet was measured according to ISO 14782 using HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd., and the total haze value is shown in the table.

[0092] Bending stiffness According to JIS P8125, a specimen cut from the sheet sample was subjected to bending load measurement at a warp angle of 15° using a V-5 Stiffness Tester (Model 150-B) manufactured by Taber Instruments Corporation, with a measurement span of 5 cm. The stiffness was calculated from the observed load.

[0093] [Diameter impact strength (high rate impact)] The dent impact strength of the test piece was measured at 0° C. using a puncture impact tester (Hydroshot HITS-P10 manufactured by Shimadzu Corporation) in accordance with JIS K7211-2. The higher the dent impact strength value, the more excellent the impact resistance.

[0094] [CO2 emissions per container upon disposal] The evaluation was carried out as a percentage (%) of the conventional P-PP container. Specifically, the evaluation was carried out using the following formula. In the case of sheet-molded products, the thickness of the conventional sheet-molded product was set to 0.4 mm, while the thickness of this product was set to 0.3 mm. In the case of injection-molded drink containers, the thickness of the side of the conventional drink container was set to 0.5 mm, while the thickness of this product was set to 0.4 mm.

[0095]

number

[0096] [Examples M1 to M4 and Comparative Examples M1 to M3] The components were blended according to the composition shown in Table 3. 0.2 parts by weight of BASF B225 as an antioxidant and 0.05 parts by weight of Dannan Chemical Industry Co., Ltd. calcium stearate as a neutralizer were added to 100 parts by weight of the total amount of B-PP and P-PP, and the mixture was stirred and mixed for 1 minute using a Henschel mixer. The mixture was melt-kneaded and extruded at a cylinder temperature of 200°C using a co-rotating twin-screw extruder TEX-30α manufactured by JSW Corporation. The strands were cooled in water and then cut with a pelletizer to obtain pellets of the polypropylene composition. An injection-molded article was obtained using the polypropylene resin composition produced in this way, and various physical properties were evaluated. The results are shown in Table 3. The evaluation methods are described below; unless otherwise specified, the same methods as in Example S were used. The same nucleating agent as used in Example S was used.

[0097] [Table 3]

[0098] [Tensile test] According to JIS K6921-2, a polypropylene composition was injection-molded into a multipurpose test piece (Type A1) according to JIS K7139 using an injection molding machine (FANUC ROBOSHOT S2000i manufactured by FANUC Corporation) under the following conditions: molten resin temperature 200°C, mold temperature 40°C, average injection speed 200 mm / s, dwell time 40 seconds, and total cycle time 60 seconds. According to JIS K7161-2, a Shimadzu Corporation precision universal testing machine (Autograph AG-X 10kN) was used to measure the tensile strength and tensile modulus at a temperature of 23°C, relative humidity of 50%, and a test speed of 1 mm / min.

[0099] [Charpy impact test] Measurements were carried out in accordance with JIS K6921-2 using a digital impact tester, model DG-UB, manufactured by Toyo Seiki Seisakusho Co., Ltd.

[0100] [Drink container flange strength F50] This was carried out using a Hydroshot HIPS-P10 (Shimadzu Corporation). Striker: 20mm diameter cylinder Impact speed: 1m / sec Using a Sumitomo Heavy Industries SE-230HY injection molding machine, drink containers (side thickness: 0.5 / 0.4mm, flange thickness: 0.7 / 0.6mm) were molded at a resin temperature of 230°C and a mold temperature of 15°C. The molded product was supported at four points as shown in Figure 1, and a striker was used to press the bottom of the container down to a certain position, impacting the flange. The test was carried out by changing the temperature in 5°C increments between -40°C and 30°C. The percentage of flanges that broke at each temperature was measured. The temperature F50, at which 50% of the containers break, was calculated using the following formula.

[0101]

number

[0102] [HDT] The test was carried out using the AUTO HDT.TESTER 6A-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. 4.6 kgf / cm 2 The deflection temperature under load was measured (in accordance with ASTM standards). [Explanation of symbols]

[0103] 1 Bottom of container 3 Fixture 5 Striker

Claims

1. A polypropylene resin composition comprising a biomass-derived polypropylene resin B-PP and a petroleum-derived polypropylene resin P-PP, The composition contains 60 to 99 parts by weight of P-PP based on 100 parts by weight of the total of the B-PP and the P-PP, The P-PP is selected from the group consisting of the following compositions (I), (II), and combinations thereof: (I): a propylene copolymer (A1) containing 15% by weight or less of ethylene or one or more C4 to C10 α-olefins; A polypropylene-based resin (A) containing an ethylene copolymer (A2) containing 16 to 25% by weight of one or more C4 to C10 α-olefins as comonomers. Including, the weight ratio of component (A1):component (A2) is 75 to 84% by weight:16 to 25% by weight; The MFR of the (A) measured at 230°C and 2.16 kg is 1.5 g / 10 min or more and less than 2.5 g / 10 min, a composition having an intrinsic viscosity of the total fraction soluble in xylene at room temperature of 0.9 to 1.5 dL / g; (II): A polypropylene resin (a) comprising an ethylene-propylene copolymer or homopolypropylene (a1) having an ethylene unit content of 1.2% by weight or less, and an ethylene-1-butene copolymer (a2) having a 1-butene unit content of 16 to 25% by weight. Including, the xylene-soluble component in (a) has an intrinsic viscosity in tetrahydronaphthalene at 135°C of 0.9 to 1.3 dl / g; The MFR of the (a) polymer, measured in accordance with JIS K 7210 at a temperature of 230°C and a weight of 2.16 kg, is 30 to 70 g / 10 min; a composition in which the content of the ethylene / 1-butene copolymer (a2) is 18 to 30% by weight when the content of the copolymer (a) is 100% by weight; The polypropylene resin composition is

2. The composition (I) further comprises a nucleating agent (C), The content of the nucleating agent (C) is 0.02 to 0.5 parts by weight per 100 parts by weight of the (A), or The composition (II) further comprises a nucleating agent (C), The content of the nucleating agent (C) is 0.02 to 0.5 parts by weight per 100 parts by weight of the (a); The polypropylene resin composition according to claim 1.

3. The polypropylene resin composition according to claim 2, wherein the nucleating agent (C) is a phosphate ester nucleating agent.

4. The method includes a step of producing the (A) through a sequential polymerization step of polymerizing a corresponding monomer to obtain the (A1) and then polymerizing a corresponding monomer in the presence of the (A1) to obtain the (A2), or With respect to (a), a step of producing the (a1) by polymerizing a corresponding monomer to obtain the (a1), and then polymerizing a corresponding monomer in the presence of the (a1) to obtain the (a2) through a sequential polymerization step is included. A method for producing the polypropylene resin composition according to any one of claims 1 to 3.

5. A sheet-shaped article obtained by molding the polypropylene resin composition according to any one of claims 1 to 3, which comprises (I) above.

6. The sheet molded article according to claim 5, having a thickness of 0.35 mm or less.

7. The sheet molded article according to claim 5, which is for use in a container.

8. The sheet molded article according to claim 6, which is for use in a container.

9. 4. An injection-molded article obtained by molding the polypropylene resin composition according to claim 1, which contains the (II).

10. 10. The injection molded article according to claim 9, wherein the thickness of the thinnest part is 1 mm or less.

11. 10. The injection-molded article according to claim 9, which is molded into the shape of a container, and the thickness of the side wall of the container is 0.1 to 1 mm.

12. The injection molded article according to claim 11, wherein the thickness of the side wall of the container is 0.1 to 0.45 mm.

13. When the dart impact strength at 0°C is I (J) and the thickness of the thinnest part of the sheet molding is t (mm), I / t≧4 The sheet molded body according to claim 5, wherein

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