JP6564224B2 - Propylene resin composition, molded body and container - Google Patents

Description

  The present invention relates to a propylene-based resin composition, a molded body formed from the composition, and a container formed from the composition.

  As a packaging container for foods such as jelly, pudding, and coffee (hereinafter, also referred to as a food packaging container), a container having excellent visibility of the contents, that is, excellent transparency, has been conventionally demanded. As a container having excellent transparency, a propylene resin composition having excellent heat resistance, rigidity and transparency is often used as a raw material.

  In addition, food is often handled in a low-temperature environment for storage and distribution, so food packaging containers are required not only to have impact resistance at room temperature but also impact resistance at low temperature, that is, low-temperature impact resistance. It is done.

  As a propylene-based resin composition having excellent impact properties, a composition containing a propylene-ethylene block copolymer, a nucleating agent, and a low-density polyethylene resin or a linear low-density polyethylene resin is known (for example, patent documents). 1).

  As a propylene-based resin composition having excellent impact properties, a composition having specific physical properties made of a propylene block copolymer and an ethylene-based resin is known (for example, see Patent Documents 2 and 3).

  Patent Document 4 discloses a propylene-based resin composition containing a specific propylene-based polymer, a specific ethylene / α-olefin copolymer, and a nucleating agent, and a molded product obtained from the composition, Containers are known.

  Conventionally, ethylene-based resins have been added to propylene-based resins in order to produce food packaging containers having excellent functions such as elastic modulus. It has been known that the transparency is inferior to that of a simple resin, and a highly transparent material containing an appropriate ethylene resin has been demanded.

JP 2001-26686 A JP 2002-187996 A Japanese Patent Laid-Open No. 2002-187997 International Publication No. 2010/074001

  The present invention has been made in view of the above-described problems of the prior art. When a molded body including a container such as a food packaging container is manufactured, the rigidity is equal to that of the conventional one, and the temperature is equal to or higher than that of the conventional one. An object of the present invention is to provide a propylene-based resin composition having impact resistance and excellent transparency, and a molded body such as a container formed from the composition.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a specific propylene-based polymer, a specific ethylene / α-olefin copolymer, and a specific propylene / ethylene copolymer are included. However, they have found that the above problems can be solved, and have completed the present invention.

  That is, the propylene-based resin composition of the present invention includes a propylene-based polymer (A) that satisfies the following requirements (A1) to (A3), an ethylene / α-olefin copolymer that satisfies the following requirements (B1) and (B2) ( B) and a propylene / ethylene copolymer (C) satisfying the following requirements (C1) and (C2).

(A1) The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) of the propylene polymer (A) is 1.5 to 4.5 (A2 ) Viscosity η ^* (frequency: 25 rad / s) measured at 210 ° C. with a rheometer of the propylene polymer (A) is 100 to 400 Pa · s. (A3) Melt flow rate (MFR) of the propylene polymer (A) ) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1 to 500 g / 10 min. (B1) The density of the ethylene / α-olefin copolymer (B) is 885 to 925 kg / m ³ . Yes (B2) Melt flow rate (MFR) of ethylene / α-olefin copolymer (B) (ASTM D-1238, measuring temperature 190 ° C., load 2. 6 kg) is 0.1 to 50 g / 10 min. (C1) Ratio of weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC) of propylene / ethylene copolymer (C) (Mw / Mn) is 1.5 to 4.5 (C2) The mol% of the structural unit derived from ethylene of the propylene / ethylene copolymer (C) is 100 mol % of the propylene / ethylene copolymer (C). The propylene-based resin composition, which is 25 to 35 mol %, has a viscosity η ^* (frequency) of the ethylene / α-olefin copolymer (B) and the propylene-based polymer (A) measured at 210 ° C. with a rheometer. : 25 rad / s) (B viscosity / A viscosity) is preferably 2.0 to 6.0.

The propylene resin composition has a viscosity η ^* (frequency: 25 rad / s) of the propylene / ethylene copolymer (C) and the ethylene / α-olefin copolymer (B) measured at 210 ° C. with a rheometer. The ratio (C viscosity / B viscosity) is preferably 1.0 to 4.0.
The molded body of the present invention is formed from the propylene-based resin composition.
The container of the present invention is formed from the propylene-based resin composition.

  The propylene-based resin composition of the present invention has a rigidity equal to the conventional one, a low temperature impact resistance equal to or higher than the conventional one when a molded body including a container such as a food packaging container is manufactured, and Transparency is better than before.

Next, the present invention will be specifically described.
The propylene resin composition of the present invention comprises a propylene polymer (A) that satisfies the following requirements (A1) to (A3), and an ethylene / α-olefin copolymer (B) that satisfies the following requirements (B1) and (B2): And a propylene / ethylene copolymer (C) that satisfies the following requirements (C1) and (C2).

(A1) The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) of the propylene polymer (A) is 1.5 to 4.5 (A2 ) Viscosity η ^* (frequency: 25 rad / s) measured at 210 ° C. with a rheometer of the propylene polymer (A) is 100 to 400 Pa · s. (A3) Melt flow rate (MFR) of the propylene polymer (A) ) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1 to 500 g / 10 min. (B1) The density of the ethylene / α-olefin copolymer (B) is 885 to 925 kg / m ³ . Yes (B2) Melt flow rate (MFR) of ethylene / α-olefin copolymer (B) (ASTM D-1238, measuring temperature 190 ° C., load 2. 6 kg) is 0.1 to 50 g / 10 min. (C1) Ratio of weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC) of propylene / ethylene copolymer (C) (Mw / Mn) is 1.5 to 4.5 (C2) The mol% of the structural unit derived from ethylene of the propylene / ethylene copolymer (C) is 100 mol % of the propylene / ethylene copolymer (C). 25-35 mol % (Propylene polymer (A))
The propylene-based resin composition of the present invention includes a propylene-based polymer (A) that satisfies the requirements (A1) to (A3). In addition, the propylene polymer (A) satisfying the requirements (A1) to (A3) is also referred to as a propylene polymer (A).

  The propylene-based polymer (A) is not particularly limited as long as it satisfies the requirements (A1) to (A3), but is usually a propylene homopolymer, propylene, and a small amount of α-olefin (provided that propylene is added). And a copolymer may be used.

In the case where the propylene polymer (A) is a propylene homopolymer or a copolymer of propylene and a small amount of an α-olefin, the structural unit is derived from all monomers constituting the propylene polymer (A). Is 100 to 100 mol%, it is preferable to have 80 to 100 mol% of structural units derived from propylene, 0 to 20 mol% of structural units derived from α-olefin, and 90 to 100 mol% of structural units derived from propylene. It is more preferable that it has 0-10 mol% of structural units derived from α-olefin.
Examples of the α-olefin include ethylene and an α-olefin having 4 to 20 carbon atoms, and ethylene and an α-olefin having 4 to 10 carbon atoms are preferable.

(Requirement (A1))
The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) of the propylene polymer (A) is 1.5 to 4.5, preferably It is 1.5 to 4.0, more preferably 2.0 to 3.5.

When Mw / Mn is in the above range, the propylene resin composition and the molded product obtained from the composition are excellent in transparency, and when it exceeds the above range, transparency tends to deteriorate and haze tends to increase. .
The propylene polymer (A) satisfying the requirement (A1) can be obtained by using a so-called single site catalyst such as a metallocene catalyst as a catalyst used during production.

(Requirement (A2))
The viscosity η ^* (frequency: 25 rad / s) measured at 210 ° C. with the rheometer of the propylene polymer (A) is 100 to 400 Pa · s, preferably 100 to 300 Pa · s. The viscosity η ^* is a temperature measured at a temperature of 210 ° C., and the temperature is in a range suitable for molding the propylene resin composition of the present invention. When the requirement (A2) is satisfied, the propylene resin composition There is a tendency that the moldability of the product is excellent.

(Requirement (A3))
The propylene polymer (A) has a melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of 1 to 500 g / 10 minutes, preferably 10 to 250 g / 10 minutes. Yes, more preferably 35 to 170 g / 10 min.

When the MFR of the propylene polymer (A) exceeds the above range, the impact resistance of the molded article such as a container obtained from the propylene resin composition of the present invention is inferior, and the MFR of the propylene polymer (A) is inferior. When the value is below the above range, the flowability of the resin in producing a molded article such as a container is inferior using the propylene-based resin composition of the present invention, and it becomes difficult to produce a thin molded article.
In addition, MFR of a propylene-type polymer (A) can be adjusted to arbitrary MFR by adjusting manufacturing conditions, such as using hydrogen as a chain transfer agent at the time of superposition | polymerization.

  In addition to the methods described above, the MFR can be adjusted by melt-kneading a propylene polymer obtained by polymerization in the presence of an organic peroxide. The MFR is increased by subjecting the propylene polymer obtained by polymerization to a melt-kneading process in the presence of an organic peroxide, and the organic peroxide when performing the melt-kneading process in the presence of the organic peroxide. MFR can be made higher by increasing the amount of addition of.

  In the case of subjecting the propylene polymer obtained by polymerization to a melt-kneading process in the presence of an organic peroxide, 0.005 to 0.05 parts by mass of the organic peroxide with respect to 100 parts by mass of the propylene polymer. It is preferable to use it.

The organic peroxide that can be used in the melt-kneading process in the presence of the organic peroxide is not particularly limited, but benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl. Peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t -Butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dichymyl peroxide, 2 , 5-Di-methyl-2,5-di- (t-butylperoxy) hexane, 2,5, -di-methyl -2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- (t-butylperoxyisopropyl) benzene, t-butylchymyl peroxide, 1,1-bis- (t -Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthane hydroper Oxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide or 2,5- Illustrative organic peroxides such as di-methyl-2,5-di- (hydroperoxy) hexane That. Of these, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferable.
The propylene polymer (A) preferably further satisfies the requirements (A4) and (A5) in addition to the requirements (A1) to (A3).

(Requirement (A4))
The propylene polymer (A) of the present invention preferably has a mmmm (pentad fraction) of 91 to 97%.

mmmm is the proportion of isotactic chains existing in pentad units in the molecular chain measured using ¹³ C-NMR, for example, as described in JP-A-2007-186664, in other words propylene This is the fraction of propylene monomer units at the center of a chain in which five monomer units are continuously meso-bonded, and can be calculated by the measurement method disclosed in the publication.
In addition, although there is no limitation in particular as measurement conditions of < ¹³ > C-NMR, it can carry out on the conditions as described in an Example, for example.

(Requirement (A5))
The propylene-based polymer (A) of the present invention preferably has a half-value width of the melting temperature (Tm) peak measured by a differential scanning calorimeter (DSC) of 5.0 to 10.0 ° C.

  The half-value width of the Tm peak is an index of the stereoregularity distribution of the propylene polymer (A). When the half-value width is within the above range, the propylene-based resin composition of the present invention and molding formed from the composition are used. Since haze of a body becomes especially small, it is preferable.

(Producing method of propylene polymer (A))
The production method of the propylene-based polymer (A) used in the present invention is not particularly limited, but it is usually obtained by polymerizing propylene in the presence of a metallocene compound-containing catalyst or in the presence of a Ziegler-Natta catalyst.

  The propylene polymer (A) is preferably obtained by polymerizing propylene in the presence of a metallocene compound-containing catalyst. When this catalyst is used, a polymer having a narrow molecular weight distribution used in the present invention can be obtained.

  In addition, when the propylene polymer (A) is a copolymer of propylene and a small amount of α-olefin (excluding propylene), a small amount of α- Olefin (but excluding propylene) is added.

(Metallocene compound-containing catalyst)
The metallocene compound-containing catalyst includes a metallocene compound, and at least one compound selected from compounds capable of reacting with an organometallic compound, an organoaluminum oxy compound, and a metallocene compound to form an ion pair, and further necessary. Accordingly, there can be mentioned a metallocene catalyst comprising a particulate carrier, preferably a metallocene catalyst capable of performing stereoregular polymerization such as isotactic or syndiotactic structure. Among the metallocene compounds, crosslinkable metallocene compounds exemplified in WO 01/27124 are preferably used, and crosslinkable metallocene compounds represented by the following general formula [I] are preferable.

上記一般式［Ｉ］において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は水素、炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよい。

In the general formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are It is selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and each may be the same or different.

  Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Linear hydrocarbon groups such as nonyl group and n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1 A branched hydrocarbon group such as a methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; Cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, tolyl group, naphthyl group, biphenyl group, A cyclic unsaturated hydrocarbon group such as an enanthryl group and an anthracenyl group; a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group such as a benzyl group, a cumyl group, a 1,1-diphenylethyl group and a triphenylmethyl group; a methoxy group And hetero atom-containing hydrocarbon groups such as ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group, and thienyl group.

  Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

Moreover, the adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring.
In the general formula [I], R ¹ , R ² , R ³ and R ⁴ substituted on the cyclopentadienyl ring are preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. More preferably, R ¹ and R ³ are hydrocarbon groups having 1 to 20 carbon atoms, and R ² and R ⁴ are hydrogen.

In the said general formula [I], it is preferable that R < ⁵ > -R < ¹² > substituted by a fluorene ring is a C1-C20 hydrocarbon group. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. The adjacent substituents of R ^{5 to} R ¹² may be bonded to each other to form a ring.

Examples of the substituted fluorenyl group (group formed by a fluorene ring and R ^{5 to} R ¹² ) constituting the metallocene compound represented by the general formula [I] include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzo A fluorenyl group, an octamethyloctahydrodibenzofluorenyl group, an octamethyltetrahydrodicyclopentafluorenyl group, etc. can be mentioned.

In the general formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element of the periodic table, more preferably carbon, silicon, or germanium, and still more preferably a carbon atom. is there. R ¹³ and R ¹⁴ substituted for Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. More preferably, R ¹³ and R ¹⁴ are aryl groups having 6 to 20 carbon atoms. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

  In the general formula [I], M is preferably a Group 4 transition metal of the periodic table, more preferably Ti, Zr, or Hf. Q is selected from the same or different combinations from halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen or an alkyl group.

  Examples of such crosslinkable metallocene compounds include diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadiene). Enyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium Dichloride, (methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3- (1 ′, 1 ′, 4 ′ , 4 ', 7', 7 ', 10', 10'-octa Tyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride (represented by the following formula [II] And a compound represented by the following formula [III] are preferred.

なお、プロピレン系重合体（Ａ）の製造に用いられるメタロセン触媒において、前記一般式［Ｉ］で表わされる架橋性メタロセン化合物とともに用いられる、有機金属化合物、有機アルミニウムオキシ化合物、および遷移金属化合物と反応してイオン対を形成する化合物、さらには必要に応じて用いられる粒子状担体については、前記国際公開第０１／２７１２４号や特開平１１−３１５１０９号公報中に開示された化合物を制限無く使用することができる。

In the metallocene catalyst used for the production of the propylene-based polymer (A), it reacts with the organometallic compound, organoaluminum oxy compound, and transition metal compound used together with the crosslinkable metallocene compound represented by the general formula [I]. As the compound that forms an ion pair, and the particulate carrier that is used as necessary, the compounds disclosed in International Publication No. 01/27124 and JP-A-11-315109 are used without limitation. be able to.

  The propylene-based polymer (A) used in the present invention polymerizes propylene or propylene and a small amount of α-olefin in the presence of the above-mentioned metallocene compound-containing catalyst or Ziegler-Natta catalyst by the method described in the examples. Can be obtained.

  The polymerization may be performed by any of a gas phase polymerization method, a liquid polymerization method such as a solution polymerization method and a suspension polymerization method, and each stage may be performed by a separate method. Moreover, you may carry out by any system of a continuous type and a semi-continuous type, and you may divide each stage into several polymerizers, for example, 2-10 polymerizers. Industrially, it is most preferable to polymerize by a continuous method.

(Ethylene / α-olefin copolymer (B))
The propylene-based resin composition of the present invention contains an ethylene / α-olefin copolymer (B) that satisfies the requirements (B1) and (B2). The ethylene / α-olefin copolymer (B) that satisfies the requirements (B1) and (B2) is also referred to as an ethylene / α-olefin copolymer (B).

  The ethylene / α-olefin copolymer (B) is not particularly limited as long as it satisfies the requirements (B1) and (B2), but ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized. Is preferable because it is excellent in impact resistance and transparency.

  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, Examples include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Of these, α-olefins having 4 to 10 carbon atoms are preferable from the viewpoints of transparency, impact resistance, rigidity, and economy.

  When the structural unit derived from all monomers constituting the ethylene / α-olefin copolymer (B) is 100 mol%, the structural unit derived from ethylene is 80 to 99 mol%, and the structural unit derived from α-olefin is 1 It is preferable to have ~ 20 mol%, more preferably 90 to 99 mol% of structural units derived from ethylene, and more preferably 1 to 10 mol% of structural units derived from α-olefin.

The ethylene / α-olefin copolymer (B) can be produced by polymerization using a so-called single site catalyst.
Examples of the single site catalyst include (a) a transition metal compound as described later, (b) an organoaluminum oxy compound, (c) a particulate carrier, and (d) a single site formed from an organoaluminum compound as required. The olefin polymerization catalyst can be used.

  When the ethylene / α-olefin copolymer (B) used in the present invention is an ethylene / α-olefin copolymer polymerized using a single site catalyst, a highly transparent propylene resin composition can be obtained. There is a tendency to be able to.

  Examples of the single site catalyst include a catalyst containing a constrained geometric complex (so-called constrained geometry catalyst (CGC) catalyst), a metallocene compound-containing catalyst, and the like. Among these, it is preferable to use a metallocene compound-containing catalyst from the viewpoint of particularly good low-temperature impact resistance.

(Requirement (B1))
The density of the ethylene / α-olefin copolymer (B) is 885 to 925 kg / m ³ , preferably 900 to 919 kg / m ³ .

  When the density of the ethylene / α-olefin copolymer (B) is lower than the above range, the rigidity and transparency of a molded body such as a container obtained from the propylene resin composition of the present invention tend to be inferior. If this is below the above range, it is presumed that the crystallinity of the ethylene / α-olefin copolymer decreases and the difference in refractive index from the propylene polymer (A) also increases.

On the other hand, when the density of the ethylene / α-olefin copolymer (B) exceeds the above range, the transparency of a molded body such as a container obtained from the propylene-based resin composition of the present invention tends to decrease. This is also because the difference in refractive index between the ethylene / α-olefin copolymer and the propylene polymer (A) is increased. That is, when the density range of the ethylene / α-olefin copolymer (B) is out of the above range, the transparency is deteriorated.
The density of the ethylene / α-olefin copolymer (B) can be adjusted to an arbitrary amount by adjusting the production conditions described later.

  More specifically, in the polymerization of the ethylene / α-olefin copolymer (B) described later, by changing the ratio of the feed amount of ethylene and α-olefin when the ethylene / α-olefin copolymer is polymerized. It can be adjusted. Specifically, by increasing the α-olefin feed amount relative to the ethylene feed amount, the density can be lowered, and the α-olefin feed amount is reduced relative to the ethylene feed amount. It is possible to increase the density.

  The density of the ethylene / α-olefin copolymer (B) is measured when the melt flow rate of the ethylene / α-olefin copolymer (B) is measured (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg). The strand obtained by heat treatment at 120 ° C. for 1 hour and slowly cooled to room temperature over 1 hour was used as a sample, the density was measured by a density gradient tube method, and an ethylene / α-olefin copolymer (B ) Density.

(Requirement (B2))
The melt flow rate (MFR) (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) of the ethylene / α-olefin copolymer (B) is 0.1 to 50 g / 10 min, preferably 1 10 to 10 g / 10 min, more preferably 2.0 to 5.0 g / 10 min.

  When the MFR of the ethylene / α-olefin copolymer (B) is below the above range, the molecular weight becomes high, so the flowability of the resin when producing a molded article such as a container is inferior, and a thin molded article is produced. When the MFR of the ethylene / α-olefin copolymer (B) exceeds the above range, the molecular weight is low and the absorbed energy for impact is low, so that it is obtained from the propylene-based resin composition of the invention. The impact resistance of the molded body such as the container is poor.

The MFR of the ethylene / α-olefin copolymer (B) can be adjusted to an arbitrary amount by adjusting the production conditions described later.
More specifically, in the polymerization of the ethylene / α-olefin copolymer (B) described later, adjustment can be made by adjusting the feed amount of hydrogen gas relative to the feed amount of ethylene and α-olefin at the time of polymerization. Is possible. It is possible to increase MFR by increasing the feed amount of hydrogen gas relative to the feed amount of ethylene and α-olefin during polymerization, and reduce the feed amount of hydrogen gas relative to the feed amount of ethylene and α-olefin. Therefore, it is possible to lower the MFR.

The viscosity η ^* (frequency: 25 rad / s) measured at 210 ° C. with the rheometer of the ethylene / α-olefin copolymer (B) is usually 200 to 2400 Pa · s, preferably 250 to 1500 Pa · s. . The viscosity η ^* is a temperature measured at a temperature of 210 ° C., and the temperature is in a range suitable for molding the propylene resin composition of the present invention, and within the above range, the propylene resin composition is molded. There is a tendency to be superior.

Hereinafter, the single-site olefin polymerization catalyst and each catalyst component used for the production of the ethylene / α-olefin copolymer (B) will be described. The (a) transition metal compound (hereinafter sometimes referred to as “component (a)”) used in the present invention is a transition metal compound represented by the following formula (I).
MLx (I)
In the formula (I), M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

  x is the valence of the transition metal atom M, and indicates the number of L coordinated to the transition metal atom. L is a ligand coordinated to the transition metal atom M, and at least two of these ligands L are a cyclopentadienyl group, a methylcyclopentadienyl group, and an ethylcyclopentadienyl group. Or a substituted cyclopentadienyl group having at least one substituent selected from hydrocarbon groups having 3 to 10 carbon atoms, and the ligand L other than the (substituted) cyclopentadienyl group is carbon It is a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group or a hydrogen atom of formulas 1-12.

  The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are methyl group, ethyl group Or it is a C3-C10 hydrocarbon group. The substituted cyclopentadienyl groups coordinated to M may be the same or different.

  Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, etc. Examples include alkyl groups; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and neophyll group.

  Of these, an alkyl group is preferable, and an n-propyl group and an n-butyl group are particularly preferable. In the present invention, the (substituted) cyclopentadienyl group coordinated to the transition metal is preferably a substituted cyclopentadienyl group, more preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms. A substituted cyclopentadienyl group is more preferred, and a 1,3-substituted cyclopentadienyl group is particularly preferred.

  In the above formula (I), the ligand L other than the (substituted) cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom. , A trialkylsilyl group or a hydrogen atom.

  Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are exemplified. Group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups Examples thereof include aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group. be able to.

Examples of the aryloxy group include a phenoxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.

  Examples of the transition metal compound represented by the general formula (I) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (N-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) Zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) Zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxychloride, bis (n- Butylcyclopentadienyl) zirconium ethoxide, bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride Bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butylcyclopentadienyl) zirconium Such as the stomach dry skull chloride, and the like. In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above-described zirconium compound can be used.

  Among these transition metal compounds represented by the general formula (I), bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl- 3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are particularly preferred.

  The organoaluminum oxy compound (b) (hereinafter sometimes referred to as “component (b)”) may be a conventionally known benzene-soluble aluminoxane, and is disclosed in JP-A-2-276807. It may be a benzene insoluble organoaluminum oxy compound.

  A conventionally known aluminoxane is, for example, an organoaluminum compound as described later and an adsorbed water, water of crystallization, ice, water vapor or the like, or an organoaluminum compound as described later and an organotin oxide. Can be made to react.

The particulate carrier (c) is an inorganic or organic compound, and a granular or particulate solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm is used. Among these, as the inorganic carrier, porous oxides are preferable. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc. or these Illustrate mixtures such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Can do. Of these, those containing as a main component at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Such a particulate carrier (c) has different properties depending on the type and production method, but the particulate carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. It is desirable that the pore volume is 0.3 to 2.5 cm ³ / g. The fine particle carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

  Furthermore, examples of the particulate carrier include granular or particulate solids of organic compounds having a particle size of 10 to 300 μm. Examples of these organic compounds include (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene. Examples thereof include a polymer or copolymer as a main component.

  The olefin polymerization catalyst used in the production of the ethylene / α-olefin copolymer (B) is formed from the above component (a), component (b) and (c) particulate carrier, but if necessary (d ) Organoaluminum compounds may be used.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as “component (d)”) used as necessary include the organoaluminum compounds represented by the following general formula (III). it can.
R ¹ _n AlX _3-n (III)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n is 1 to 3).

In the general formula (III), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, n- Examples thereof include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

  Specific examples of such organoaluminum compounds include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (d), a compound represented by the following general formula (IV) can also be used.
R ¹ _n AlY _3-n (IV)
In the formula (IV), R ¹ represents the same hydrocarbon as R ¹ in the general formula (III), and Y represents —OR ² group, —OSiR ³ ₃ group, —OAlR ⁴ ₂ group, —NR ⁵ _2. A group, —SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to 2, and R ² , R ³ , R ⁴ and R ⁸ are methyl group, ethyl group, isopropyl group, An isobutyl group, a cyclohexyl group, a phenyl group, and the like, R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, and the like, and R ⁶ and R ⁷ are a methyl group, an ethyl group, and the like. . )
Among such organoaluminum compounds, compounds represented by R ¹ _n Al (OAlR ⁴ ₂ ) _{3 -n} , such as Et ₂ AlOAlEt ₂ and (iso-Bu) ₂ AlOAl (iso-Bu) ₂ are preferable. .

Among the organoaluminum compounds represented by the general formulas (III) and (IV), a compound represented by the general formula R ¹ ₃ Al is preferable, and a compound in which R ¹ is an isoalkyl group is particularly preferable.

  When the ethylene / α-olefin copolymer (B) is produced, the component (a), the component (b) and the fine particle carrier (c) as described above are brought into contact with each other as necessary. The prepared catalyst is used.

  Contact of each of the above components can be carried out in an inert hydrocarbon solvent. Specifically, as the inert hydrocarbon medium used for the preparation of the catalyst, propane, butane, pentane, hexane, heptane, octane, decane, Aliphatic hydrocarbons such as dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated carbonization such as ethylene chloride, chlorobenzene and dichloromethane Examples thereof include hydrogen or a mixture thereof.

  The catalyst used for the production of the ethylene / α-olefin copolymer (B) is the presence of the component (a), the component (b), the particulate carrier (c) and, if necessary, the component (d). It may be a prepolymerization catalyst obtained by prepolymerizing an olefin below. The prepolymerization is performed by introducing an olefin into an inert hydrocarbon solvent in the presence of the component (a), the component (b), the particulate carrier (c), and the component (d) as necessary. It can be carried out.

  Examples of the olefin used in the prepolymerization include ethylene and the same α-olefin having 3 to 20 carbon atoms as described above. Among these, ethylene used in the polymerization or a combination of ethylene and an α-olefin having 3 to 20 carbon atoms is particularly preferable.

  The prepolymerization can be performed either batchwise or continuously, and can be performed under reduced pressure, normal pressure, or increased pressure. In the prepolymerization, the preliminary viscosity [η] measured in decalin at least 135 ° C. in the presence of hydrogen is in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g. It is desirable to produce a polymer.

  The ethylene / α-olefin copolymer (B) is obtained by polymerizing ethylene in the gas phase in the presence of the olefin polymerization catalyst or the prepolymerization catalyst as described above, or ethylene and an α-olefin having 3 to 20 carbon atoms. Is obtained by copolymerization in the gas phase. Further, it is possible to introduce a chain transfer agent represented by hydrogen gas as necessary, and to adjust the molecular weight of the polymer to be produced. As a result, the melt flow rate (MFR) (ASTM D-1238, It is possible to adjust the measurement temperature 190 ° C. and the load 2.16 kg).

In the polymerization, the olefin polymerization catalyst or the prepolymerization catalyst as described above is usually 10 ⁻⁸ to 10 ⁻³ gram atom / liter, preferably 10 ⁻⁷ to 10 in terms of the concentration of transition metal atoms in the polymerization reaction system. It is preferably used in an amount of 10 ^-4 gram atoms / liter.

  In the polymerization, the same organoaluminum oxy compound and / or organoaluminum compound (d) as in component (b) may be added. At this time, the atomic ratio (Al / M) of the aluminum atom (Al) derived from the organoaluminum oxy compound and the organoaluminum compound to the transition metal atom (M) derived from the transition metal compound (a) is 5 to 300. , Preferably 10 to 200, more preferably 15 to 150.

The polymerization temperature is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is usually from atmospheric pressure 100 kg / cm ^2, and preferably a pressurized condition of to 50 kg / cm ^2, the polymerization is a batch, semi-continuous, be carried out by any of the methods of continuous it can.
Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The ethylene / α-olefin copolymer (B) is produced by carrying out the above steps, but the requirement (B1) relating to the ethylene / α-olefin copolymer (B) is ethylene and α-olefin in the polymerization step. It can be adjusted by adjusting the ratio of the feed amount. The density can be lowered by increasing the α-olefin feed amount relative to the ethylene feed amount, and the density can be reduced by reducing the α-olefin feed amount relative to the ethylene feed amount. It can be raised.

  Regarding the requirement (B2) regarding the ethylene / α-olefin copolymer (B), when ethylene or ethylene and α-olefin are fed in the above polymerization step, the ethylene and α-olefin are fed as a chain transfer agent. Adjustment is possible by changing the ratio of the feed amount of hydrogen gas. In the case of feeding ethylene or α-olefin, ethylene / α-olefin copolymer (B) melt by increasing the amount of hydrogen gas to ethylene and α-olefin. The flow rate (MFR) (ASTM D-1238, measuring temperature 190 ° C., load 2.16 kg) is increased, and the feed rate of ethylene or the feed rate of ethylene and α-olefin when ethylene and α-olefin are fed. On the other hand, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) of the ethylene / α-olefin copolymer (B) is lowered by reducing the feed amount of hydrogen gas.

(Propylene / ethylene copolymer (C))
The propylene-based resin composition of the present invention includes a propylene / ethylene copolymer (C) that satisfies the requirements (C1) and (C2).
The propylene / ethylene copolymer (C) satisfying the requirements (C1) and (C2) is also referred to as a propylene / ethylene copolymer (C).

The propylene / ethylene copolymer (C) is not particularly limited as long as it satisfies the requirements (C1) and (C2). The propylene / ethylene copolymer (C) has a structural unit derived from propylene and a structural unit derived from ethylene, but may have a structural unit derived from an α-olefin having 4 or more carbon atoms.
The α-olefin having 4 or more carbon atoms is preferably at least one α-olefin selected from 1-butene, 1-hexene, and 1-octene.

(Requirement (C1))
The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) of the propylene / ethylene copolymer (C) is 1.5 to 4.5, preferably Is 2.0 to 3.5. The propylene resin composition of the present invention comprising the propylene / ethylene copolymer (C) having such a molecular weight distribution is excellent in transparency, impact resistance and the like.

(Requirement (C2))
The mol% of the structural unit derived from ethylene of the propylene / ethylene copolymer (C) is 25 to 35 mol %, preferably 25 to 30 mol % in 100 mol % of the propylene / ethylene copolymer (C). It is.

Propylene-ethylene copolymer (C) in 100 mol%, mol% of constitutional unit derived from propylene is usually a 65 to 75 mol%, preferably 70-75 [mol%. Moreover, when it has a structural unit derived from an α-olefin having 4 or more carbon atoms, the mol% derived from the α-olefin having 4 or more carbon atoms is usually 5 to 30 mol %, preferably 10 to 25 mol. %.

The viscosity η ^* (frequency: 25 rad / s) measured at 210 ° C. with the rheometer of the propylene / ethylene copolymer (C) is usually 600 to 3000 Pa · s, preferably 700 to 2800 Pa · s. The viscosity η ^* is a temperature measured at a temperature of 210 ° C., and the temperature is in a range suitable for molding the propylene resin composition of the present invention, and within the above range, the propylene resin composition is molded. There is a tendency to be superior.

  The propylene / ethylene copolymer (C) according to the present invention is not particularly limited, but is preferably produced in the presence of a single site catalyst such as a metallocene compound-containing catalyst. Examples of the metallocene compound-containing catalyst used in the production of the propylene / ethylene copolymer (C) include a metallocene compound, and a compound that can react with an organometallic compound, an organoaluminum oxy compound, and a metallocene compound to form an ion pair. A metallocene compound-containing catalyst comprising at least one compound selected from the above, and, if necessary, a particulate carrier. As the metallocene compound, for example, a crosslinkable metallocene compound represented by the above general formula [1] can be used. As the metallocene compound or the metallocene compound-containing catalyst, those already disclosed in International Publication No. 01/27124 or JP-A-11-315109 by the present applicant are preferably used.

(Nucleating agent)
The propylene-based resin composition of the present invention includes a propylene-based polymer (A), an ethylene / α-olefin copolymer (B), and a propylene / ethylene copolymer (C), but further includes a nucleating agent. May be.

  The nucleating agent contained in the propylene resin composition of the present invention is not particularly limited, but a sorbitol nucleating agent, a phosphorus nucleating agent, a carboxylic acid metal salt nucleating agent, a polymer nucleating agent, an inorganic A compound or the like can be used. As the nucleating agent, a sorbitol nucleating agent, a phosphorus nucleating agent, or a polymer nucleating agent is preferably used. Nucleating agents may be used alone or in combination of two or more.

  Examples of sorbitol nucleating agents include nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] (nonitol 1,2,3-trideoxy- 4,6: 5,7-bis-O-[(4-propylphenyl) methylene]), 1,3,2,4-dibenzylidenesorbitol, 1,3,2,4-di- (p-methylbenzylidene) Sorbitol and 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol can be used.

  Examples of phosphorus nucleating agents include sodium-bis- (4-t-butylphenyl) phosphate, potassium bis- (4-t-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis ( 4,6-di-t-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, bis (2,4,8,10-tetra) -T-Butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide salt can be used.

As the carboxylic acid metal salt nucleating agent, for example, pt-butyl benzoic acid aluminum salt, aluminum adipate, sodium benzoate can be used.
A branched α-olefin polymer is preferably used as the polymer nucleating agent. Examples of branched α-olefin polymers include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene. 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, a homopolymer of 3-ethyl-1-hexene, or a copolymer thereof, and May include copolymers of these and other α-olefins. A polymer of 3-methyl-1-butene is particularly preferable from the viewpoints of transparency, low-temperature impact resistance, good rigidity characteristics, and economical efficiency.

As the inorganic compound, for example, talc, mica, calcium carbonate can be used.
Among these nucleating agents, nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[((from the viewpoint of transparency, low temperature impact resistance, rigidity and low odor) 4-propylphenyl) methylene] and / or bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin It is preferable to use a 6-oxide) aluminum hydroxide salt.

  As the nucleating agent used in the present invention, commercially available products can be used. For example, nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene ] Is commercially available under the trade name Millard NX8000 (made by Milliken), and ADK STAB NA-21 (trade name, made by ADEKA) is bis (2,4,8,10-tetra-t-butyl-6- Hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) It is commercially available as a nucleating agent containing an aluminum hydroxide salt as a main component.

  When the propylene-based resin composition of the present invention contains a nucleating agent, the molded article such as a container formed from the composition of the present invention tends to be excellent in rigidity and transparency. This is presumed to be due to an improvement in transparency due to a reduction in the spherulite size of crystals in the propylene-based resin composition and a reduction in diffused reflection of light, and an increase in rigidity due to an improvement in crystallinity.

  If the content of the nucleating agent in the propylene-based resin composition is less than the following range, the effect of improving the rigidity and transparency is insufficient, and if the content of the nucleating agent is more than the following range, the further improving effect is Little and not economical.

[Propylene resin composition]
The propylene resin composition of the present invention contains a propylene polymer (A), an ethylene / α-olefin copolymer (B), and a propylene / ethylene copolymer (C). The content of each component of the propylene-based resin composition is such that the total of the propylene-based polymer (A), the ethylene / α-olefin copolymer (B) and the propylene / ethylene copolymer (C) is 100 parts by mass. The propylene polymer (A) is usually 57 to 80 parts by mass, the ethylene / α-olefin copolymer (B) is 17 to 40 parts by mass, and the propylene / ethylene copolymer (C) is 3 to 20 parts by mass. Preferred are 62 to 75 parts by mass of the propylene polymer (A), 22 to 35 parts by mass of the ethylene / α-olefin copolymer (B), and 3 to 10 parts by mass of the propylene / ethylene copolymer (C). When the propylene resin composition contains a nucleating agent, the content of the propylene polymer (A), the ethylene / α-olefin copolymer (B), and the propylene / ethylene copolymer (C). When the total is 100 parts by mass, it is usually 0.1 to 0.5 parts by mass, preferably 0.1 to 0.4 parts by mass.

  Further, the propylene-based resin composition of the present invention is appropriately neutralized, antioxidant, heat stabilizer, weathering agent, lubricant, ultraviolet absorber, antistatic agent, antiblocking as long as the object of the present invention is not impaired. Agents, antifogging agents, antifoaming agents, dispersants, flame retardants, antibacterial agents, fluorescent brighteners, cross-linking agents, cross-linking aids, degraving agents (organic peroxides); coloring dyes, pigments, etc. Other components such as an agent may be included.

  When the propylene resin composition of the present invention contains other components, the total amount of the propylene polymer (A) and the ethylene / α-olefin copolymer (B) is 100 parts by mass. It is contained in the range of 0.0001 to 10 parts by mass.

  The propylene resin composition of the present invention preferably has a melt flow rate (MFR) (measuring temperature 230 ° C., load 2.16 kg) of 20 to 200 g / 10 minutes, preferably 25 to 140 g / 10 minutes. It is more preferable, and it is still more preferable that it is 30-80 g / 10min. In the said range, since it is excellent in the fluidity | liquidity at the time of shape | molding molded objects, such as a container, using a propylene-type resin composition, it is preferable.

  The MFR of the propylene-based resin composition is the melt flow rate (MFR) of the propylene-based polymer (A) constituting the propylene-based resin composition (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg), or ethylene Adjustment is possible by appropriately selecting the melt flow rate (MFR) (ASTM D-1238, measurement temperature 190 ° C., load 2.16 kg) of the α-olefin copolymer (B).

  In addition to the methods described above, adjustment can be made by coexisting an organic peroxide when each component is melt-kneaded with a kneader. That is, the MFR of the propylene-based resin composition can be increased by adding an organic peroxide during melt-kneading or increasing the amount of the organic peroxide added during melt-kneading. The organic peroxide that can be used in the present invention is not particularly limited, but is benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-oxide. -Methyl-2,5-di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-diperadipate, t- Butylperoxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dichymyl peroxide, 2,5-di-methyl-2,5 -Di- (t-butylperoxy) hexane, 2,5, -di-methyl-2,5-di- (t-butylper) Xy) hexyne-3,1,3-bis- (t-butylperoxyisopropyl) benzene, t-butylchymyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene Hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide or 2,5-di-methyl-2,5-di- (hydro Organic peroxides such as peroxy) hexane can be exemplified. Of these, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferable. When using an organic peroxide, it is used in the range of 0.005 to 0.05 parts by mass with respect to 100 parts by mass in total of the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B). It is preferable.

The propylene-based resin composition of the present invention preferably has a tensile modulus of 700 to 1700 MPa, and more preferably 900 to 1500 MPa.
The tensile elastic modulus of the propylene-based resin composition of the present invention is obtained by injection-molding the composition at a cylinder temperature of 210 ° C. and a mold temperature of 40 ° C. using an injection molding machine having a clamping force of 40 tons. It is measured using the test piece for tensile modulus obtained. Specific methods for measuring the tensile modulus of the propylene-based resin composition include the methods described in the examples below.

Propylene resin composition of the present invention, the Charpy impact strength was measured by the method described in Example, is preferably 1.5 kJ / m ² or more, more preferably 1.7kJ / m ² or more . Although there is no limitation in particular as an upper limit, Usually, it is 4.0 kJ / m < ² > or less.

  In the propylene-based resin composition of the present invention, the haze measured by the method described in Examples is preferably 15% or less, and more preferably 13% or less. There is no particular limitation on the lower limit.

  When the tensile elastic modulus of the propylene-based resin composition of the present invention is within the above range, the molded body including a container such as a food packaging container has a high rigidity and a large load even if it is thinner and lighter than before. Even if it takes, it is preferable because it is difficult to deform.

  The propylene-based resin composition of the present invention has a so-called sea-island structure in which the propylene-based polymer (A) is mainly a continuous phase, that is, a sea phase. The ethylene / α-olefin copolymer (B) mainly constitutes an island phase. For this reason, the propylene-based resin composition of the present invention can achieve both high rigidity and impact resistance. The propylene / ethylene copolymer (C) is preferably present at the interface between the propylene-based polymer (A) and the ethylene / α-olefin copolymer (B). Become transparent.

(Viscosity ratio)
The propylene resin composition of the present invention has a viscosity η ^* (frequency: 25 rad / s) of an ethylene / α-olefin copolymer (B) and a propylene polymer (A) measured at 210 ° C. with a rheometer. The ratio (viscosity of B / viscosity of A) is usually 2.0 to 6.0, preferably 2.0 to 5.5, more preferably 2.5 to 5.0.

If it exceeds this range, the haze of the propylene-based resin composition deteriorates. On the other hand, if it falls below this range, the MFR of the propylene-based resin composition becomes extremely low, which is not desirable.
The propylene-based resin composition of the present invention has a viscosity η ^* (frequency: measured with a rheometer at 210 ° C. of the propylene / ethylene copolymer (C) and the ethylene / α-olefin copolymer (B). 25 rad / s) (viscosity of C / viscosity of B) is usually 1.0 to 4.4, preferably 1.0 to 4.0, more preferably 1.0 to 3. 0, particularly preferably 1.0 to 2.0.

If this range is exceeded, the haze of the propylene-based resin composition may deteriorate.
The viscosity of each of the propylene polymer (A), the ethylene / α-olefin copolymer (B), and the propylene / ethylene copolymer (C) should be measured using a rheometer at a temperature of 210 ° C. and a frequency of 25 rad / s. Is possible.

When the propylene-based resin composition is molded, a phase structure is formed in which the island phase formed from the ethylene / α-olefin copolymer (B) is dispersed in the sea phase formed from the propylene-based polymer (A). The ratio of the viscosity η ^* (frequency: 25 rad / s) measured at 210 ° C. with a rheometer between the propylene / ethylene copolymer (C) and the ethylene / α-olefin copolymer (B) is within the above range. And propylene / ethylene copolymer (C) is not dispersed alone in the sea phase formed from propylene polymer (A), but propylene polymer (A) and ethylene / α-olefin copolymer The propylene / ethylene copolymer (C) is disposed at the interface with (B), which tends to be more excellent in transparency, which is preferable.

  When the propylene-based resin composition of the present invention is injection-molded, the island structure differs between the vicinity of the surface of the molded body and the interior of the molded body. Specifically, in the portion close to the surface, the island structure is flat (a flat shape in which the depth direction of the molded body is short), and approaches a spherical shape inside the molded body. Since the island structure near the surface of the molded body is flat, light scattering in the portion is suppressed and the internal haze is reduced. For this reason, the molded object of this invention is excellent in transparency. Moreover, the effect which makes an internal haze small can be exhibited more by using the polymer obtained by the single site catalyst as a propylene polymer (A).

  Since the propylene-based resin composition of the present invention includes the above-described components in the above ranges, when a molded body such as a food packaging container is manufactured, the rigidity is equal to the conventional value, or the It has the above-mentioned low-temperature impact resistance and is more excellent in transparency than before.

  Although the manufacturing method of the propylene-type resin composition of this invention is not specifically limited, As this manufacturing method, the method of melt-kneading each component with a kneader, for example and manufacturing a propylene-type resin composition is mentioned. Examples of the kneader include a single-screw kneading extruder, a multi-shaft kneading extruder, a kneader, a Banbury mixer, and a Henschel mixer. The melt-kneading conditions are not particularly limited as long as the molten resin does not deteriorate due to shearing during kneading, heating temperature, heat generation due to shearing, and the like. From the viewpoint of preventing the deterioration of the molten resin, it is effective to set the heating temperature appropriately or to add an antioxidant or a heat stabilizer.

  Various molded products can be obtained by molding the propylene-based resin composition of the present invention according to a known molding technique. Molding technologies include, for example, injection molding, injection stretch blow molding, compression molding, injection compression molding, T-die film molding, stretched film molding, inflation film molding, sheet molding, calendar molding, pressure molding, vacuum molding, pipe molding, and atypical. Examples include extrusion molding, hollow molding, and laminate molding.

As a molded object formed from the propylene-type resin composition of this invention, a container, household appliance parts, daily necessities, etc. are mentioned. Among these, containers are preferable from the viewpoint of impact resistance and rigidity.
The container of the present invention is formed from the propylene-based resin composition described above. Containers include liquid containers for daily necessaries such as shampoos, hair preparations, cosmetics, detergents, and disinfectants; food packaging containers for liquids such as soft drinks, water, and seasonings; solids such as jelly, pudding, and yogurt It can be used in a wide range of packaging containers for foods; packaging containers for other chemicals; packaging containers for industrial liquids.

In particular, it can be suitably used as a food packaging container that is required to be thinner and lighter than conventional ones and that is excellent in the visibility of contents and is required to have less odor.
The container (for example, food packaging container) formed from the propylene-based resin composition of the present invention is preferably obtained by injection molding or injection stretch blow molding.

As a method of injection molding, for example, molding can be performed by the following method using an injection molding machine. First, a propylene resin composition is introduced into a hopper of an injection mechanism, and the propylene resin composition is fed into a cylinder heated to approximately 200 ° C. to 250 ° C., and is kneaded and plasticized to be in a molten state. This is a metal mold closed at a high pressure and high speed (maximum pressure 700-1500 kg / cm ³ ) from a nozzle and controlled at 5-50 ° C., preferably 30-50 ° C. by cooling water or warm water, etc. Injection into the mold. It can be carried out by cooling and solidifying the propylene-based resin composition injected by cooling from the mold, opening the mold with a mold clamping mechanism, and obtaining a molded product.

As an injection stretch blow molding, for example, a propylene-based resin composition is introduced into a hopper of an injection molding machine, the resin is fed into a cylinder heated to about 200 ° C. to 250 ° C., kneaded and plasticized to be in a molten state. To do. This is a metal mold closed by a mold clamping mechanism which is adjusted to a temperature of 5 to 50 ° C., preferably 10 to 30 ° C. with cooling water or hot water at high pressure and high speed (maximum pressure 700 to 1500 kg / cm ³ ) from the nozzle. It is injection molded into a mold, where it is cooled for 1.0 to 3.0 seconds to form a preform, then immediately the mold is opened and stretched and oriented in the longitudinal direction using a stretching rod, and further in the transverse direction by blow molding. It can be performed by stretching and orientation to obtain a molded product.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
[Evaluation method]
According to the method described below, the physical properties of the propylene polymer (A), the ethylene / α-olefin copolymer (B), the propylene / ethylene copolymer (C) and the propylene resin composition were measured.

[Melt flow rate (MFR)]
MFR was measured according to ASTM D 1238 at 230 ° C. or 190 ° C. with a 2.16 kg load.

[density]
The density was measured by the following method.
A strand obtained by measuring the melt flow rate (ASTM D-1238) of the ethylene / α-olefin copolymer (B) at a measurement temperature of 190 ° C. under a load of 2.16 kg (ASTM D-1238) is heat-treated at 120 ° C. for 1 hour, What was gradually cooled to room temperature over time was used as a sample, and the density was measured by a density gradient tube method.

[viscosity]
The density was measured using a rheometer (PHYSICA MCR301 manufactured by Anton Paar Japan).
Measurement conditions were set as follows.
Sample: Press plate 28mmφ × 1mm
Measuring jig: Plate-plate gap: 0.8mm
Measurement temperature: 210 ° C
Measurement frequency: 25 rad / s

[Molecular weight distribution]
For the molecular weight analysis of the polymer, GPC analysis was performed under the following conditions, and the molecular weight distribution (Mw / Mn) was calculated.
Apparatus: Waters Alliance GPC 2000 type column: TSKgel GMH6-HTx2 TSKgel GMH6-HTLx2 (both manufactured by Tosoh Corporation, inner diameter 7.5 mm x length 30 cm)
Column temperature: 140 ° C
Mobile phase: orthodichlorobenzene (containing 0.025% dibutylhydroxytoluene)
Detector: differential refractometer flow rate: 1.0 mL / min
Sample concentration: 0.15% (w / v)
Injection volume: 0.5 mL
Sampling time interval: 1 second Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation).

[Stereoregularity]
Pentad fraction (mmmm: [%])
The pentad fraction (mmmm,%) of the propylene-based polymer (A) was calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on Macromolecules 8,687 (1975). ^{The 13} C-NMR spectrum was measured using an EX-400 device manufactured by JEOL, based on TMS, using a temperature of 130 ° C. and an o-dichlorobenzene solvent.

[Stereoregularity distribution DSC half width]
The full width at half maximum of the melting temperature (Tm) peak of the propylene polymer (A) was determined by DSC measurement under the following conditions.

  Using a differential scanning calorimeter [SII RDC220], a sample of about 10 mg was heated from 30 ° C. to 230 ° C. at a heating rate of 500 ° C./min in a nitrogen atmosphere and held at that temperature for 10 minutes. Furthermore, after cooling to 50 ° C. at a temperature lowering rate of 10 ° C./min and holding at that temperature for 5 minutes, the temperature was raised to 190 ° C. at a temperature rising rate of 10 ° C./min. The endothermic peak observed during the second temperature increase was taken as the melting peak, the temperature was determined as the melting temperature (Tm), and the half width of the peak was derived.

[Ethylene ratio]
The ratio ( mol %) of the structural unit derived from ethylene of the propylene / ethylene copolymer (C) was calculated from the peak intensity ratio of the ¹³ C-NMR spectrum.
^{The 13} C-NMR spectrum was measured using an EX-400 device manufactured by JEOL, based on TMS, using a temperature of 130 ° C. and an o-dichlorobenzene solvent.

[Haze]
The haze of the square plate test piece for haze measurement obtained in each comparative example was measured using NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the haze test method defined in JIS K7136.
As the test piece, a test piece having a length of 60 mm, a width of 60 mm, and a thickness of 1 mm obtained by injection molding described later was used. This haze evaluation result was used as an index of transparency. That is, a small value was considered excellent in transparency.

[Tensile modulus]
The tensile elastic modulus of the test piece for measuring the tensile elastic modulus obtained in each example and comparative example was measured under the following measurement conditions in accordance with the tensile elastic modulus test method defined in JIS K7202.
<Measurement conditions>
Temperature: 23 ° C
Test piece: JIS K7162-BA dumbbell
5mm (width) x 2mm (thickness) x 75mm (length)
Tensile speed: 1.0 mm / min Distance between spans: 58 mm

[Low temperature impact resistance]
A Charpy impact test was performed in accordance with JIS K7111 under the following conditions to determine Charpy impact strength [kJ / m ² ].
<Test conditions>
Temperature: 0 ° C
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
Single notch, edgewise vertical, notch machined

[Production of Propylene Polymer (A1)]
(1) Production of Solid Catalyst Support 300 g of SiO ₂ (Sunsphere H121 manufactured by AGC S-Itech) was sampled in a 1 L branch flask, and 800 mL of toluene was added to make a slurry. Next, the solution was transferred to a 5 L four-necked flask, and 260 mL of toluene was added. 2830 mL of methylaluminoxane (hereinafter MAO) -toluene solution (10 wt% solution) was introduced. The mixture was stirred for 30 minutes while remaining at room temperature. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on carrier)
[3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl in a 5 L four-necked flask in a glove box ) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] 1.0 g of zirconium dichloride was weighed. The flask was taken out, 0.5 L of toluene and 2.0 L of MAO / SiO ₂ / toluene slurry prepared in (1) above (100 g as a solid component) were added under nitrogen, and the mixture was stirred for 30 minutes to carry.

  The obtained [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride / MAO / SiO2 / toluene slurry was 99% substituted with n-heptane and the final slurry amount was 4. It was 5 liters. This operation was performed at room temperature. Thereafter, the solid content (solid catalyst component) was recovered.

(3) Production of prepolymerization catalyst 101 g of the solid catalyst component prepared in the above (2), 111 mL of triethylaluminum, and 80 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C. and 303 g of ethylene was inserted And allowed to react with stirring for 180 minutes.

  After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration would be 1 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization Into a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 30 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in (3) above is 3.2 g / hour as a solid catalyst component, triethyl Aluminum was supplied continuously at 1.0 ml / hour and polymerized in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 50 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.10 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G. Subsequently, the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L, and further polymerization was performed. To the polymerization vessel, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.10 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G. Furthermore, the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 12 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.10 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G. Finally, the obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 13 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.10 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G to obtain a propylene polymer at 40 kg / hour.

After vaporizing the obtained slurry, gas-solid separation was performed, and the slurry was introduced into a conical dryer and vacuum-dried at 80 ° C.
The propylene-based polymer thus obtained has an MFR (230 ° C., load 2.16 kg) of 4.0 g / 10 min, a pentad fraction (mmmm) of 95%, and a Tm peak half-value width of 3.3. C. and Mw / Mn were 3.0.

The obtained propylene polymer was processed using a degra agent (Kayahexa AD; Kayaku Akzo Co., Ltd.) to obtain a propylene polymer (A1). The propylene polymer (A1) has an MFR (230 ° C., load 2.16 kg) of 103 g / 10 min, a viscosity η ^* (frequency: 25 rad / s) (210 ° C.) of 210 Pa · s, and Mw / Mn of 2.2. The pentad fraction (mmmm) was 95%, and the half width of the Tm peak was 8.5 ° C.

[Production of ethylene / α-olefin copolymer (B)]
(Preparation of catalyst)
Into a 300 liter reactor sufficiently purged with nitrogen, 10.0 kg of silica dried at 600 ° C. for 10 hours and 154 liter of toluene were charged, suspended, and cooled to 0 ° C. Thereafter, 23.4 liters of a toluene solution of methylaminoxan (Al = 3.02 mol / liter) was added dropwise to the suspension over 1 hour. At this time, the temperature in the system was kept in the range of 0 to 5 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make a total volume of 160 liters.

  To the suspension thus obtained, 20.0 liters of a toluene solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride (Zr = 25.6 mmol / liter) was added at 35 ° C. The mixture was added dropwise over 30 minutes and further reacted at 35 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst component (1) containing 3.2 mg of zirconium per 1 g of the solid catalyst component.

(Preparation of prepolymerization catalyst)
A 350 liter reactor sufficiently purged with nitrogen was charged with 7.0 kg of the solid catalyst component (1) prepared above and hexane to make the total volume 285 liters. After cooling the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 Nm ³ / hr for 5 minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, the ethylene supply was stopped, and 2.4 mol of diisobutylaluminum hydride (DIBALH) and 1.2 kg of 1-hexene were charged. After the inside of the system was closed, ethylene supply was started again at a flow rate of 8 Nm ³ / hr. After 15 minutes, the ethylene flow rate was lowered to 2 Nm ³ / hr, and the pressure in the system was adjusted to 0.08 MPaG. During this time, the temperature in the system rose to 35 ° C. Thereafter, ethylene was supplied at a flow rate of 4 Nm ³ / hr for 3.5 hours while adjusting the temperature in the system to 32 to 35 ° C. During this time, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and washed twice with hexane. Thus, a prepolymerized catalyst (2) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component was obtained.

(polymerization)
Using a continuous fluidized bed gas phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a total pressure of 2.0 MPaG, a polymerization temperature of 80 ° C., and a gas linear velocity of 0.7 m / sec.

Polymerization was started while continuously feeding 4.1 g / hr of the prepolymerized catalyst (2) prepared above and triisobutylaluminum (TIBA) at a rate of 5 mmol / hr.
In order to maintain a constant gas composition during the polymerization, ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied (gas composition; 1-hexene / ethylene = 0.03, hydrogen / ethylene = 4.2 × 10 ^-4 , ethylene concentration = 71%). The yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the density was 913 kg / m ³ , the MFR (230 ° C., load 2.16 kg) was 6.2 g / 10 min, MFR (190 ° C., load 2.16 kg) was 3.3 g / 10 min, and viscosity η ^* (frequency: 25 rad / s) (210 ° C.) was 746 Pa · s.
The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B1).

[Production of propylene / ethylene copolymer (C1)]
A metallocene catalyst compound ((8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5) is fed from a supply port of a continuous polymerization vessel having a volume of 300 liters. , 6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride)) at 0.026 mmol / hr, modified methylaluminoxane at 6.5 mmol / hr, triisobutylaluminum at 3.5 mmol / hr, It was continuously fed with toluene (total 33 L / hr).

  Simultaneously, 15 kg / hr of propylene, 2.7 kg / hr of ethylene and 4 L / hr of hydrogen are continuously fed from another feed port of the polymerization vessel, polymerization temperature 60 ° C., total pressure 1.3 MPaG, residence time 100 Continuous solution polymerization was conducted under the conditions of minutes.

  The toluene solution of propylene / ethylene copolymer produced in the polymerization vessel was heated to remove toluene. As a result, a propylene / ethylene copolymer was obtained at a production speed of 11.1 kg / h.

The propylene / ethylene copolymer (C1) obtained had an MFR (230 ° C., load 2.16 kg) of 10 g / 10 min, an ethylene content of 28 mol%, a viscosity η ^* (frequency: 25 rad / s) of 961 Pa · s, Mw / Mn was 3.

[Production of propylene / ethylene copolymer (C2)]
A metallocene catalyst compound ((8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5) is fed from a supply port of a continuous polymerization vessel having a volume of 300 liters. , 6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride)) at 0.023 mmol / hr, modified methylaluminoxane at 5.8 mmol / hr, triisobutylaluminum at 3.1 mmol / hr, It was continuously fed with toluene (total 33 L / hr).

  Simultaneously, 15 kg / hr of propylene, 3.1 kg / hr of ethylene and 2 L / hr of hydrogen are continuously fed from another feed port of the polymerization vessel, polymerization temperature 60 ° C., total pressure 1.3 MPaG, residence time 100 Continuous solution polymerization was conducted under the conditions of minutes.

  The toluene solution of propylene / ethylene copolymer produced in the polymerization vessel was heated to remove toluene. As a result, a propylene / ethylene copolymer was obtained at a production speed of 9.3 kg / h.

The propylene / ethylene copolymer (C2) obtained had an MFR (230 ° C., load 2.16 kg) of 6 g / 10 min, an ethylene content of 26 mol%, a viscosity η ^* (frequency: 25 rad / s) of 1640 Pa · s, Mw / Mn was 3.

[Production of propylene / ethylene copolymer (C3)]
A metallocene catalyst compound ((8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5) is fed from a supply port of a continuous polymerization vessel having a volume of 300 liters. , 6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride)) at 0.020 mmol / hr, modified methylaluminoxane at 5.0 mmol / hr, triisobutylaluminum at 2.7 mmol / hr, It was continuously fed with toluene (total 33 L / hr).

  At the same time, 14 kg / hr of propylene, 2.1 kg / hr of ethylene and 1 L / hr of hydrogen are continuously fed from another supply port of the polymerization vessel, polymerization temperature 60 ° C., total pressure 1.3 MPaG, residence time 100 Continuous solution polymerization was conducted under the conditions of minutes.

  The toluene solution of propylene / ethylene copolymer produced in the polymerization vessel was heated to remove toluene. As a result, a propylene / ethylene copolymer was obtained at a production speed of 8.01 kg / h.

The propylene / ethylene copolymer (C3) obtained had an MFR (230 ° C., load 2.16 kg) of 2 g / 10 min, an ethylene content of 24 mol%, a viscosity η ^* (frequency: 25 rad / s) of 3250 Pa · s, Mw. / Mn was 3.

[Production of propylene / ethylene copolymer (C4)]
The same method as C1-3 is applied, MFR (230 ° C., load 2.16 kg) is 1 g / 10 min, ethylene content is 24 mol%, viscosity η ^* (frequency: 25 rad / s) is 4540 Pa · s, Mw / Mn Was adjusted to 3 to obtain a propylene / ethylene copolymer (C4).

[Reference Example 1]
100 parts by mass of the propylene polymer (A1), 0.3 parts by mass of Millard NX8000 (manufactured by Milliken) as the nucleating agent, and phosphorus antioxidant [Tris (2,4-di-t- Butylphenyl) phosphite], 0.19 parts by weight of calcium stearate as a neutralizing agent, 0.07 parts by weight of erucic acid amide as a lubricant, Kayahexa AD (Kayaku Akzo Co., Ltd.) as a degraving agent The mixture was stirred and mixed with 0.12 part by mass of a Henschel mixer, and the mixture was melt-kneaded under the following conditions using a twin screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. to obtain a strand.
The resulting strand was cooled with water and then cut with a pelletizer to obtain a propylene-based resin composition pellet (1).

(Twin screw extruder conditions)
Model: NR-36
Screw rotation speed 250rpm
Resin temperature 200 ℃
Using the obtained pellet (1), the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.

  From the obtained pellet (1), using an electric injection molding machine with a clamping force of 40 tons (series model EC40NII manufactured by Toshiba Machine) under the conditions of a cylinder temperature of 210 ° C. and a mold temperature of 40 ° C., a length of 60 mm, a width A test piece having a thickness of 60 mm and a thickness of 1 mm was injection molded to obtain a square plate test piece for haze measurement.

Under the same conditions, a tensile elastic modulus test piece (JIS K7162-BA) (5 mm (width) x 2 mm (thickness) x 75 mm (length)), a Charpy impact strength test piece (10 mm (width) x 80 mm ( Length) × 4 mm (thickness)).
Using these test pieces, haze, tensile modulus, and Charpy impact strength (single notch, edgewise perpendicular, temperature 0 ° C.) were measured. The results are shown in Table 4.

[Reference Example 2]
Except having changed the quantity of the nucleating agent from 0.3 mass part to 0.41 mass part, it carried out similarly to the reference example 1, and obtained the pellet (2) of the propylene-type resin composition.

  The resulting propylene-based resin composition pellet (2) was mixed with 73 parts by mass and the ethylene / α-olefin copolymer (B1) was mixed with 27 parts by mass. The resulting mixture was a twin-screw extruder manufactured by Toyo Seiki Seisakusho. (Laboplast mill micro) was used to melt and knead to obtain a strand, which was further cut with a pelletizer to obtain a propylene-based resin composition pellet (3).

Using the obtained pellet (3), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (3), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.
(Twin screw extruder conditions)
Model: Laboplast mill micro screw rotation speed 45rpm
Resin temperature 200 ℃

[Example 1]
Except having changed the quantity of the nucleating agent from 0.3 mass part to 0.43 mass part, it carried out similarly to the reference example 1, and obtained the pellet (4) of the propylene-type resin composition.

  69 parts by mass of the resulting propylene-based resin composition pellet (4), 25 parts by mass of ethylene / α-olefin copolymer (B1), and 6 parts by mass of propylene / ethylene copolymer (C1) were mixed. The mixture was melt-kneaded using a twin-screw extruder manufactured by Toyo Seiki Seisakusho Co., Ltd. (Laboplast Mill Micro) to obtain a strand, which was further cut with a pelletizer, and the propylene resin composition pellets (5) were obtained. Obtained.

Using the obtained pellet (5), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (5), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.
(Twin screw extruder conditions)
Model: Laboplast mill micro screw rotation speed 45rpm
Resin temperature 200 ° C

[Comparative Example 1]
70 parts by mass of propylene-based resin composition 1 (J13BP; manufactured by Prime Polymer), 30 parts by mass of propylene-based resin composition 2 (J105P; manufactured by Prime Polymer), and Millard NX8000 (manufactured by Milliken) as a nucleating agent. 0.3 parts by mass, 0.1 parts by mass of a phosphorus-based antioxidant [tris (2,4-di-t-butylphenyl) phosphite] as an additive, and 0.09 parts by mass of calcium stearate as a neutralizing agent Part, 0.07 part by mass of erucic acid amide as a lubricant was mixed with a Henschel mixer, and the mixture was subjected to the same conditions as in Reference Example 1 using a twin screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. A melt was kneaded to obtain a strand.

The resulting strand was cooled with water and then cut with a pelletizer to obtain a propylene-based resin composition pellet (6).
Using the obtained pellet (6), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (6), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 2]
Except having changed the quantity of the nucleating agent from 0.3 mass part to 0.41 mass part, it carried out similarly to the comparative example 1, and obtained the pellet (7) of the propylene-type resin composition.

  73 parts by mass of the propylene-based resin composition pellet (7) and 27 parts by mass of the ethylene / α-olefin copolymer (B1) were mixed and melt-kneaded in the same manner as in Reference Example 2 to obtain a strand. And was cut with a pelletizer to obtain a pellet (8) of a propylene-based resin composition.

Using the resulting pellet (8), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene resin composition was measured. The results are shown in Table 4.
About the obtained pellet (8), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 3]
Except having changed the quantity of the nucleating agent from 0.3 mass part to 0.43 mass part, it carried out similarly to the comparative example 1, and obtained the pellet (9) of the propylene-type resin composition.

  69 parts by mass of the propylene-based resin composition pellet (9), 25 parts by mass of the ethylene / α-olefin copolymer (B1), and propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) Six parts by mass were mixed and melt-kneaded in the same manner as in Example 1 to obtain a strand, which was cut with a pelletizer to obtain a propylene-based resin composition pellet (10).

Using the obtained pellet (10), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (10), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

Toughmer S4020 is PER polymerized using a Ziegler-Natta catalyst, MFR (230 ° C.) is 2 g / 10 min, ethylene content is 31 mol %, viscosity η ^* (frequency: 25 rad / s) is 2430 Pa · s and Mw / Mn were 5 .

[Comparative Example 4]
Propylene resin composition pellets (11) were prepared in the same manner as in Comparative Example 3 except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) was changed to the propylene / ethylene copolymer (C1). Obtained.

Using the obtained pellet (11), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (11), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 5]
Propylene resin composition pellets (12) were produced in the same manner as in Comparative Example 3 except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) was changed to the propylene / ethylene copolymer (C2). Obtained.

Using the resulting pellet (12), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (12), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 6]
Propylene resin composition pellets (13) were prepared in the same manner as in Comparative Example 3 except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) was changed to the propylene / ethylene copolymer (C3). Obtained.

Using the obtained pellet (13), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (13), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 7]
A propylene-based resin composition was prepared in the same manner as in Comparative Example 3 except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) was changed to a propylene / ethylene copolymer (Tuffmer S4030, manufactured by Mitsui Chemicals). Pellet (14) was obtained.

Using the resulting pellet (14), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (14), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

Toughmer S4030 is PER polymerized using a Ziegler-Natta catalyst, MFR (230 ° C., load 2.16 kg) is 0.4 g / 10 min, ethylene content is 31 mol%, viscosity η ^* (frequency : 25 rad / s) was 4870 Pa · s, and Mw / Mn was 5.

[Comparative Example 8]
Propylene resin composition 1 (J13BP; manufactured by Prime Polymer Co., Ltd.) was changed from 70 parts by mass to 100 parts by mass, and propylene resin composition 2 (J105P; manufactured by Prime Polymer Co., Ltd.) was changed from 30 parts by mass to 0 parts by mass. The same procedure as in Comparative Example 3 was conducted except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals, Inc.) was changed to a propylene / ethylene copolymer (C4). )

Using the resulting pellet (15), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (15), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 9]
The propylene resin composition 1 (J13BP; manufactured by Prime Polymer Co., Ltd.) was changed from 70 parts by mass to 85 parts by mass, and the propylene resin composition 2 (J105P; manufactured by Prime Polymer Co., Ltd.) was changed from 30 parts by mass to 15 parts by mass. The same procedure as in Comparative Example 3 was conducted except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) was changed to the propylene / ethylene copolymer (C4). )

Using the obtained pellet (16), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (16), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 10]
Propylene resin composition pellets (17) were carried out in the same manner as in Comparative Example 3 except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) was changed to the propylene / ethylene copolymer (C4). Obtained.

Using the resulting pellet (17), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (17), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

[Comparative Example 11]
The propylene resin composition 1 (J13BP; manufactured by Prime Polymer Co., Ltd.) was changed from 70 parts by mass to 52 parts by mass, and the propylene resin composition 2 (J105P; manufactured by Prime Polymer Co., Ltd.) was changed from 30 parts by mass to 48 parts by mass. The same procedure as in Comparative Example 3 was conducted except that the propylene / ethylene copolymer (Tuffmer S4020; manufactured by Mitsui Chemicals) was changed to a propylene / ethylene copolymer (C4). )

Using the resulting pellet (18), the melt flow rate MFR (230 ° C., load 2.16 kg) of the propylene-based resin composition was measured. The results are shown in Table 4.
About the obtained pellet (18), it shape | molded by the method similar to the reference example 1, the test piece was obtained, and each physical property was evaluated. The results are shown in Table 4.

  The physical properties of the propylene-based polymers used in Reference Examples, Examples and Comparative Examples are shown in Table 1, the physical properties of the ethylene / α-olefin copolymer are shown in Table 2, and the physical properties of the propylene / ethylene copolymer are shown in Table 3. Table 4 shows the physical properties and evaluation results of the propylene resin compositions obtained in Reference Examples, Examples, and Comparative Examples.

  In Table 1, the descriptions of J13BP: J105P = 70: 30, J13BP: J105P = 85: 15, J13BP: J105P = 52: 48 indicate that the mass ratio between J13BP and J105P is 70:30 and 85:15, respectively. , 52:48.

  The physical properties of the mixture of J13BP and J105P were such that J13BP and J105P were stirred and mixed with a Henschel mixer at a predetermined mass ratio, and the mixture was used with a twin-screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. The strands obtained by melt-kneading under the same conditions as in Reference Example 1 were measured.

From the examples and comparative examples 1 to 4, it can be seen that the propylene-based resin composition of the present invention has low haze (excellent transparency) while maintaining the properties of excellent tensile modulus and Charpy impact strength.
Further, from Examples and Comparative Examples 3 and 5 to 11, the optimum ranges of the above-described viscosity ratios (B viscosity / A viscosity) and (C viscosity / B viscosity) are known.

Claims (5)

Propylene polymer (A) satisfying the following requirements (A1) to (A3), ethylene / α-olefin copolymer (B) satisfying the following requirements (B1) and (B2), the following requirements (C1) and (C2 A propylene-based resin composition containing a propylene / ethylene copolymer (C) satisfying
(A1) The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) of the propylene polymer (A) is 1.5 to 4.5 (A2 ) Viscosity η ^* (frequency: 25 rad / s) measured at 210 ° C. with a rheometer of the propylene polymer (A) is 100 to 400 Pa · s. (A3) Melt flow rate (MFR) of the propylene polymer (A) ) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1 to 500 g / 10 min. (B1) The density of the ethylene / α-olefin copolymer (B) is 885 to 925 kg / m ³ . Yes (B2) Melt flow rate (MFR) of ethylene / α-olefin copolymer (B) (ASTM D-1238, measuring temperature 190 ° C., load 2. 6 kg) is 0.1 to 50 g / 10 min. (C1) Ratio of weight average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC) of propylene / ethylene copolymer (C) (Mw / Mn) is 1.5 to 4.5 (C2) The mol% of the structural unit derived from ethylene of the propylene / ethylene copolymer (C) is 100 mol % of the propylene / ethylene copolymer (C). 25-35 mol % Ratio of the viscosity η ^* (frequency: 25 rad / s) of the ethylene / α-olefin copolymer (B) and the propylene polymer (A) measured at 210 ° C. with a rheometer (B viscosity / A viscosity) ) Is 2.0 to 6.0. The propylene-based resin composition according to claim 1. Ratio of viscosity η ^* (frequency: 25 rad / s) of propylene / ethylene copolymer (C) and ethylene / α-olefin copolymer (B) measured at 210 ° C. with a rheometer (C viscosity / B The propylene-based resin composition according to claim 1 or 2, wherein the viscosity of the propylene-based resin composition is 1.0 to 4.0.   The molded object formed from the propylene-type resin composition as described in any one of Claims 1-3.   The container formed from the propylene-type resin composition as described in any one of Claims 1-3.