JP6887349B2 - Polypropylene composition - Google Patents

Description

The present invention relates to polypropylene compositions, and more particularly to polypropylene compositions that provide a sheet or film with excellent transparency, rigidity, and impact resistance.

Polypropylene has excellent physical properties and is also excellent in hygiene, so it is useful as a packaging application for food containers and the like. In food containers, transparency is required so that the contents can be confirmed. Further, the food container is required to have high impact resistance, particularly high impact resistance at low temperature, so that the food can be transported and stored at low temperature while being contained therein. Furthermore, in order to improve storage stability, the food container is also required to have high rigidity.

Patent Document 1 provides a sheet having excellent transparency, impact resistance, and rigidity by subjecting a composition composed of polypropylene and an ethylene-α-olefin copolymer containing no crystal nucleating agent to a specific quenching step. It is disclosed that it was manufactured. Further, Patent Document 2 and Patent Document 3 disclose that a polypropylene composition containing a crystal nucleating agent was used to produce a sheet having excellent transparency and rigidity.

Patent No. 46944475 JP 2015-000960 Japanese Unexamined Patent Publication No. 2015-053678

The composition described in Patent Document 1 is subject to a manufacturing method restriction that it is subjected to a specific quenching step. However, a composition that imparts excellent transparency, impact resistance, and rigidity without being subject to such manufacturing restrictions has higher industrial utility value. Further, the sheets obtained in Patent Document 2 and Patent Document 3 have a problem that the impact resistance at low temperature is not always sufficient. In view of such circumstances, it is an object of the present invention to provide a polypropylene composition that provides a sheet or film having excellent transparency, impact resistance, and rigidity.

The inventors have found that certain polypropylene compositions solve the above problems. That is, the above-mentioned problem is solved by the following invention.
[1] A propylene (co) polymer containing 0 to 2% by weight of ethylene as the component (A),
The component (B) contains a copolymer of ethylene and an α-olefin having 8 or more carbon atoms, and the component (C) contains a crystal nucleating agent.
The MFR (230 ° C., 2.16 kg) of the component (A) is 0.3 to 10 g / 10 minutes, and the polydisperse index is 5 to 10.
The density of the copolymer of the component (B) is 0.890 to 0.915 g / cm ³ , and the MFR (190 ° C., 2.16 kg) is 0.5 to 5 g / 10 minutes.
The weight ratio of component (A): component (B) is 90 to 99.5: 0.5 to 10.
A total of 100 parts by weight of the component (A) and the component (B) contains 0.015 to 0.5 parts by weight of the component (C).
Polypropylene composition.
[2] The component (A) corresponds to a solid catalyst containing an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component, and a catalyst containing an organoaluminum compound. The composition according to [1], which is a propylene (co) polymer obtained by polymerizing a monomer.
[3] The composition according to [1] or [2], wherein the α-olefin in the component (B) has 8 carbon atoms.
[4] The composition according to any one of [1] to [3], wherein the ethylene content in the component (A) is 0.3 to 2% by weight.
[5] The composition according to any one of [1] to [4], wherein the MFR (230 ° C., 2.16 kg) of the component (A) is 2 to 7 g / 10 minutes.
[6] A sheet or film produced from the composition according to any one of the above [1] to [5].

INDUSTRIAL APPLICABILITY The present invention can provide a polypropylene composition that provides a sheet or film having excellent transparency, impact resistance, and rigidity.

In the present invention, the sheet is a member having a thickness of 200 μm or more, and the film is a member having a thickness of less than 200 μm. In the present invention, a sheet or film may be referred to as "sheet or the like". Further, in the present invention, "X to Y" includes values at both ends, that is, X and Y.

1. 1. Polypropylene composition The polypropylene composition of the present invention contains the following components.
Component (A): Propylene (co) polymer containing 0 to 2% by weight of ethylene,
Component (B): A copolymer of ethylene and an α-olefin having 8 or more carbon atoms,
Component (C): Crystal nucleating agent

(1) Ingredient (A)
The component (A) is a propylene (co) polymer containing 0 to 2% by weight of ethylene. The fact that the copolymer contains 0% by weight of ethylene means that it is homopolypropylene. Further, the fact that the copolymer contains 2% by weight of ethylene means that the amount of ethylene-derived units in the copolymer is 2% by weight. The same applies to other copolymers. If the amount of ethylene exceeds the upper limit, the rigidity of a sheet or the like decreases. Further, when the amount of ethylene is 0.3 to 2% by weight, the transparency of a sheet or the like is improved, which is preferable. From this viewpoint, the amount of ethylene is more preferably 0.3 to 1.5% by weight.

The MFR of the component (A) at 230 ° C. and a load of 2.16 kg is 0.3 to 10 g / 10 minutes. If the MFR is less than the lower limit, the load on the molding machine becomes high during molding of the sheet or the like and the moldability is lowered, and if it exceeds the upper limit, drawdown is likely to occur and the secondary moldability is lowered. From this point of view, the MFR is preferably 2 to 7 g / 10 minutes.

The multivariance index (PI) of component (A) is 5-10. The polydispersity index is an index of the molecular weight distribution, and is obtained from the complex elastic modulus by measuring the viscoelasticity. Specifically, G '(storage modulus) and G "crossover modulus when (loss modulus) of the same value (unit: Pa) was used as a Gc, calculated from the equation PI = ¹⁰ 5 / Gc If the PI is less than the lower limit, drawdown is likely to occur and the secondary formability is lowered, and if the PI is more than the upper limit, it becomes difficult to manufacture the component (A) itself and the appearance of the sheet or the like is deteriorated. Therefore, the PI is preferably 5 to 7.

The density of the component (A) is not limited, but is preferably about ^{0.890 to 0.915 g / cm 3.}

The component (A) may be produced by any method, but a solid catalyst containing an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component, and a catalyst containing an organoaluminum compound may be used. It is preferably produced by polymerizing the corresponding monomer. By manufacturing in this way, the rigidity of the sheet or the like can be improved. Further, by manufacturing in this manner, the multivariance index (PI) can be within the above range.

(2) Ingredient (B)
The component (B) is a copolymer of ethylene and an α-olefin having 8 or more carbon atoms. The density of the copolymer is 0.890 to 0.915 g / cm ³ . The density greatly affects the transparency of a sheet or the like, and the transparency of the sheet or the like decreases even if it is below the lower limit or exceeds the upper limit. The amount of α-olefin is adjusted to achieve this density. The α-olefin is not limited as long as it has 8 or more carbon atoms, but it is preferably 8 or 9 carbon atoms, preferably 1-octene, from the viewpoint of economic availability such as industrial availability and cost. More preferred. When an α-olefin having 8 carbon atoms is used, the amount in the copolymer is about 15 to 30% by weight.

The MFR of component (B) at 190 ° C. and a load of 2.16 kg is 0.5 to 5 g / 10 minutes. MFR has a great influence on the transparency of a sheet or the like, and the transparency of the sheet or the like is lowered even if it is less than the lower limit or exceeds the upper limit.

The density of the component (B) and the MFR have a great influence on the transparency of the sheet or the like. The reason for this is not limited, but when the density of the component (B) and the MFR are in the above range, the balance between the density of the component (A) and the MFR is improved, and the transparency is improved when the sheet or the like is used. It is presumed that this is because the structure can be achieved.

(3) Ingredient (C)
The crystal nucleating agent is not particularly limited, and those usually used in the art may be used, but a nonitol-based nucleating agent, a sorbitol-based nucleating agent, a phosphate ester-based nucleating agent, a triaminobenzene derivative-based nucleating agent, and a carboxylic acid. It is preferable to select from an acid metal salt-based nucleating agent and an organic nucleating agent such as a xylitol-based nucleating agent. Examples of the nonitol-based nucleating agent include 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol. Examples of the sorbitol-based nucleating agent include 1,3: 2,4-bis-o- (3,4-dimethylbenzylidene) -D-sorbitol. Examples of the phosphoric acid ester-based nucleating agent include phosphoric acid 2,2'-methylenebis (4,6-di-t-butylphenyl) sodium salt and phosphoric acid-2,2'-methylenebis (4,6-di-tert). Examples thereof include aromatic phosphate ester-based nucleating agents such as −butylphenyl) aluminum salt and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) lithium salt. Examples of the triaminobenzene derivative-based nucleating agent include 1,3,5-tris (2,2-dimethylpropanamide) benzene. Examples of the metal carboxylate-based nucleating agent include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate, and diparat-. Examples thereof include aluminum butyl benzoate, titanium di-para-t-butyl benzoate, chromium di-para-t-butyl benzoate, and aluminum hydroxy-di-t-butyl benzoate. Examples of xylitol-based nucleating agents include bis-1,3: 2,4- (5', 6', 7', 8'-tetrahydro-2-naphthaldehydebenzylidene) 1-allylxylitol, bis-1,3: 2,4- (3', 4'-dimethylbenzylidene) 1-propylxylitol can be mentioned. The above crystal nucleating agent may be used alone or in combination of two or more.

In the present invention, the crystal nucleating agent can be blended by using a master batch composed of the crystal nucleating agent and the olefin polymer. When the matrix polymer of the masterbatch contains the component (A) or the component (B), the amount of the masterbatch so that the weight ratio of the component (A): component (B) in the polypropylene composition of the present invention is in the range described later. And the concentration of crystal nucleating agent in the masterbatch is adjusted. When the matrix polymer does not contain the component (A) or the component (B), the polypropylene composition of the present invention will contain the matrix polymer as another component described later.

(4) Composition ratio The weight ratio of the component (A): component (B) in the polypropylene composition of the present invention is "90 to 99.5": "0.5 to 10". If the weight ratio of the component (A) is less than the lower limit, the rigidity of the sheet or the like is lowered, and if it exceeds the upper limit, the impact resistance of the sheet or the like is lowered. If the weight ratio of the component (B) is less than the lower limit, the impact resistance of the sheet or the like is lowered, and if it exceeds the upper limit, the rigidity of the sheet or the like is lowered and the economy is also lowered. From this viewpoint, the weight ratio of the component (B) is preferably 1 to 10.

The composition of the present invention contains 0.015 to 0.5 parts by weight of the component (C) with respect to a total of 100 parts by weight of the component (A) and the component (B). If the amount of the component (C) added is less than the lower limit, the transparency of the sheet or the like is lowered, and if it exceeds the upper limit, the economic efficiency is lowered. From this viewpoint, the amount of the component (C) added is preferably 0.015 to 0.45 parts by weight.

(5) Other Ingredients The polypropylene composition of the present invention contains antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, and antistatic agents. Commonly used for olefin polymers such as fogging agents, flame retardants, dispersants, copper damage inhibitors, neutralizers, plasticizers, bubble inhibitors, crosslinkers, peroxides, oil spreads and other organic and inorganic pigments. Conventional additives may be added. The amount of each additive added may be a known amount. Further, as described above, in the present invention, the crystal nucleating agent can be blended by using the master batch composed of the olefin polymer and the crystal nucleating agent. If the matrix polymer of the masterbatch is different from the components (A) and (B), the polypropylene composition of the present invention may contain the matrix polymer.

2. Method for Producing Polypropylene Composition 1) Ingredient (A)
As described above, the component (A) contains the raw material monomer, a solid catalyst containing magnesium, titanium, halogen, and a succinate compound as an internal electron donor compound, an organoaluminum compound, and if necessary, an external electron donor compound. It is preferably produced by a method including a step of polymerizing using a catalyst.

A polymer polymerized using a catalyst containing a succinate compound as an internal electron donor compound (hereinafter, also referred to as “Suc catalyst”) has a wide molecular weight distribution (high PI) and a uniform high molecular weight component and low molecular weight component. It is dispersed in. The molecular weight distribution is a physical quantity and can be determined by measurement. However, this measured value cannot represent the degree of dispersion of the high molecular weight component and the low molecular weight component. For example, by melt-kneading the high molecular weight component and the low molecular weight component given in the powder or pellet properties using an extruder or the like, or by performing multistage polymerization of components having different molecular weights using a catalyst other than the Suc catalyst, at first glance , It is also possible to obtain a polymer having a molecular weight distribution (measured value) equivalent to that of the polymer obtained by polymerization using a Suc catalyst. However, the degree of dispersion of the high molecular weight component and the low molecular weight component is different between the polymer thus obtained and the polymer obtained by polymerization using a Suc catalyst, and the latter achieves a uniform degree of dispersion. The difference is remarkable in performance such as rigidity, impact resistance, workability, and appearance.

1-1) Solid catalyst (component (i))
The component (i) can be prepared by a known method, for example, by bringing the magnesium compound, the titanium compound and the electron donor compound into mutual contact.

As the titanium compound used for the preparation of the component (i), a tetravalent titanium compound represented by _{the general formula: Ti (OR) g} X _{4-g is suitable.} In the formula, R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4. As titanium compounds, TiCl ₄ and more specifically, TiBr _4, titanium tetrahalides such as _{TiI 4; Ti (OCH 3)} Cl 3, Ti (OC 2 H 5) Cl 3, Ti (O n -C 4 H ₉ ) _{Trihalogenated alkoxytitanium such as Cl 3} , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl _{2, Ti (O n -C 4} H 9) 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated alkoxy titanium such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl _{, Ti (O n -C 4 H} 9) 3 Cl, Ti (OC 2 H 5) monohalide trialkoxy titanium such as _{3 Br; Ti (OCH 3)} 4, Ti (OC 2 H 5) 4, Ti ( such as O _n -C ₄ tetraalkoxy titanium such as H _{9) 4} and the like. Among these, a halogen-containing titanium compound, particularly titanium tetrahalogenate, is preferable, and titanium tetrachloride is particularly preferable.

Examples of the magnesium compound used for the preparation of the component (i) include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, and dihexylmagnesium. Examples thereof include decyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxymagnesium, ethyl butyl magnesium, and butyl magnesium hydride. These magnesium compounds can be used in the form of a complex compound with, for example, organoaluminum, and may be in a liquid state or a solid state. More suitable magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; magnesium methoxychloride, magnesium ethoxychloride, magnesium isopropoxychloride, magnesium butoxychloride, magnesium octoxychloride. Alkoxymagnesium halide; Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; phenoxy Alyloxymagnesium such as magnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate can be mentioned.

The electron donor compound used for the preparation of component (i) is generally referred to as an "internal electron donor compound". In the present invention, it is preferable to use an internal electron donor compound that gives a wide molecular weight distribution. Generally, it is known that the molecular weight distribution can be increased by polymer blending or polymerizing in multiple steps, but the composition polymerized using the catalyst is a powder or a polymer polymerized using another catalyst. It exhibits excellent rigidity, impact resistance, processability, appearance, etc. as compared with a composition having the same molecular weight distribution obtained by blending in pellet properties and a composition having the same molecular weight distribution by multistage polymerization. This is because the composition produced by using the catalyst is integrated with the high molecular weight component and the low molecular weight component in a state close to the molecular level, but the latter composition is not mixed in a state close to the molecular level. It is considered that this is because they only seem to show the same molecular weight distribution. However, it is not realistic to express this in words in the claims. Hereinafter, preferred internal electron donor compounds will be described.

The preferred internal electron donor compound in the present invention is a succinate compound. In the present invention, the succinate compound refers to a succinic acid diester or a substituted succinic acid diester. Hereinafter, the succinate compound will be described in detail. The succinate-based compound preferably used in the present invention is represented by the following formula (I).

In the formula, the groups R ₁ and R ₂ are linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkyl from _{C 1 to} C ₂₀ , which are the same or different from each other and may contain heteroatoms. Aryl groups; groups R _{3 to} R ₆ are linear or branched alkyl, alkenyl, cycloalkyl, aryl, of _{C 1 to} C ₂₀ , which are identical or different from each other and contain hydrogen or, in some cases, heteroatoms. _{Groups R 3 to} R ₆ , which are arylalkyl or alkylaryl groups and are bonded to the same carbon atom or different carbon atoms, may be bonded together to form a ring.

R ₁ and R ₂ are preferably C _1- C ₈ alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Compounds in which R ₁ and R ₂ are selected from primary alkyls, particularly branched primary alkyls, are particularly preferred. Examples of suitable R ₁ and R ₂ groups are C _1- C ₈ alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.

One of the preferred groups of compounds represented by formula (I) is branched alkyl, cycloalkyl, aryl, arylalkyl _{, where R 3 to} R ₅ are hydrogen and R _{6 has 3 to 10 carbon atoms.} , And an alkylaryl group. Preferred specific examples of such a monosubstituted succinate compound are diethyl-sec-butyl succinate, diethyl texyl succinate, diethyl cyclopropyl succinate, diethyl norbonyl succinate, diethyl perihydro succinate, diethyl. Trimethylsilyl succinate, diethyl methoxy succinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexyl Methyl succinate, diethyl-t-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopentyl succinate, diethyl (1-trifluoromethyl ethyl) succinate , Diethylfluorenyl succinate, 1-ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyltexyl succinate, diisobutylcyclopropyl succinate, diisobutylnorbonyl succinate, diisobutylperihydro Succinate, diisobutyltrimethylsilyl succinate, diisobutylmethoxysuccinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutylcyclohexylsuccinate, diisobutylbenzyl succinate, diisobutylcyclohexylmethyl Succinate, diisobutyl-t-butyl succinate, diisobutylisobutyl succinate, diisobutylisopropyl succinate, diisobutylneopentyl succinate, diisobutylisopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, Diisobutylfluorenyl succinate, dineopentyl-sec-butyl succinate, dineopentyltexyl succinate, geneopentylcyclopropyl succinate, dineopentyl norbonyl succinate, dineopentyl perihydrosuccinate , Dineopentyltrimethylsilyl succinate, dineopentylmethoxysuccinate, geneopentyl-p-methoxyphenyl succinate, geneopentyl-p-chlorophenyl succinate, geneopentylphenyl succinate, genine Opentyl Cyclohexyl succinate, Dineopentyl benzyl succinate, Dineopentyl cyclohexylmethyl succinate, Dineopentyl-t-butyl succinate, Dineopentyl isobutyl succinate, Dineopentyl isopropyl succinate, Di Neopentyl neopentyl succinate, dineopentyl isopentyl succinate, dineopentyl (1-trifluoromethylethyl) succinate, dineopentyl fluorenyl succinate.

Another preferred group of compounds within the range of formula (I) is a _{linear C 1 to} C ₂₀ in which _{at least two groups from R 3 to} R ₆ differ from hydrogen and in some cases contain heteroatoms. Alternatively, it is selected from branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups. A compound in which two groups different from hydrogen are bonded to the same carbon atom is particularly preferable. Specifically, it is a compound in which _{R 3} and R ₄ are different groups from hydrogen, and R ₅ and R _{6 are hydrogen atoms.} Preferred specific examples of such disubstituted succinates are diethyl-2,2-dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diethyl-2-benzyl-2-isopropylsuccinate, diethyl. -2-Cyclohexylmethyl-2-isobutylsuccinate, diethyl-2-cyclopentyl-2-n-butylsuccinate, diethyl-2,2-diisobutylsuccinate, diethyl-2-cyclohexyl-2-ethylsuccinate Nate, diethyl-2-isopropyl-2-methylsuccinate, diethyl-2-tetradecyl-2-ethylsuccinate, diethyl-2-isobutyl-2-ethylsuccinate, diethyl-2- (1-trifluoro) Methylethyl) -2-methylsuccinate, diethyl-2-isopentyl-2-isobutylsuccinate, diethyl-2-phenyl-2-n-butylsuccinate, diisobutyl-2,2-dimethylsuccinate, Diisobutyl-2-ethyl-2-methylsuccinate, diisobutyl-2-benzyl-2-isopropylsuccinate, diisobutyl-2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl-2-cyclopentyl-2-n- Butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2-cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methylsuccinate, diisobutyl-2-tetradecyl-2- Ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl-2- (1-trifluoromethylethyl) -2-methyl succinate, diisobutyl-2-isopentyl-2-isobutyl succinate , Diisobutyl-2-phenyl-2-n-butyl succinate, dineopentyl-2,2-dimethylsuccinate, dineopentyl-2-ethyl-2-methylsuccinate, dineopentyl-2-benzyl-2-isopropyls Xinate, Dineopentyl-2-cyclohexylmethyl-2-isobutyl succinate, Dineopentyl-2-cyclopentyl-2-n-butyl succinate, Dineopentyl-2,2-diisobutyl succinate, Dineopentyl-2-cyclohexyl-2 -Ethyl succinate, dineopentyl-2-isopropyl-2-methyl succinate, dineopentyl-2-tetradecyl-2-ethyl succine , Dineopentyl-2-isobutyl-2-ethyl succinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methylsuccinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl It is -2-phenyl-2-n-butyl succinate.

Further, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are also particularly preferable. Specifically, it is _{a compound in which R 3} and R ₅ are different groups from hydrogen. In this case, R ₄ and R ₆ may be hydrogen atoms or groups different from hydrogen, but it is preferable that one of them is a hydrogen atom (trisubstituted succinate). Preferred specific examples of such compounds are diethyl-2,3-bis (trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2- (3,3,3-). Trifluoropropyl) -3-methylsuccinate, diethyl-2,3-bis (2-ethylbutyl) succinate, diethyl-2,3-diethyl-2-isopropylsuccinate, diethyl-2,3-diisopropyl-2 -Methyl succinate, diethyl-2,3-dicyclohexyl-2-methyldiethyl-2,3-dibenzylsuccinate, diethyl-2,3-diisopropylsuccinate, diethyl-2,3-bis (cyclohexylmethyl) ) Succinate, diethyl-2,3-di-t-butyl succinate, diethyl-2,3-diisobutyl succinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diiso Pentyl succinate, diethyl-2,3- (1-trifluoromethylethyl) succinate, diethyl-2,3-tetradecyl succinate, diethyl-2,3-fluorenyl succinate, diethyl-2-isopropyl -3-Isobutyl succinate, diethyl-2-tert-butyl-3-isopropyl succinate, diethyl-2-isopropyl-3-cyclohexyl succinate, diethyl-2-isopentyl-3-cyclohexyl succinate, diethyl -2-Tetradecyl-3-cyclohexylmethyl succinate, diethyl-2-cyclohexyl-3-cyclopentyl succinate, diisobutyl-2,3-diethyl-2-isopropylsuccinate, diisobutyl-2,3-diisopropyl-2 -Methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methyl succinate, diisobutyl-2,3-dibenzylsuccinate, diisobutyl-2,3-diisopropylsuccinate, diisobutyl-2,3- Bis (cyclohexylmethyl) succinate, diisobutyl-2,3-di-t-butyl succinate, diisobutyl-2,3-diisobutyl succinate, diisobutyl-2,3-dineopentyl succinate, diisobutyl-2, 3-Diisopentyl succinate, diisobutyl-2,3- (1-trifluoromethylethyl) succinate, diisobutyl-2,3-tetradecyl succinate, diisobutyl-2,3-fluorenyl succinate , Diisobutyl-2-isopropyl-3-isobutyl succinate, diisobutyl-2-tert-butyl-3-isopropyl succinate, diisobutyl-2-isopropyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3-3 Cyclohexyl succinate, diisobutyl-2-tetradecyl-3-cyclohexylmethyl succinate, diisobutyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,3-bis (trimethylsilyl) succinate, dineopentyl-2,2- sec-Butyl-3-methylsuccinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methylsuccinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, dineopentyl- 2,3-Diethyl-2-isopropyl succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3-di Benzyl succinate, dineopentyl-2,3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2,3- Diisobutyl succinate, geneopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl-2 , 3-Tetradecyl succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl-3-isopropyl succinate, dineopentyl -2-Isopropyl-3-cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, dineopentyl-2-cyclohexyl-3-cyclopentyl succinate Nate.

Among the compounds of formula (I), a compound some are bonded to form a ring together of the radicals R ₃ to R ₆ may be also preferably used. As such compounds, the compounds listed in Special Table 2002-542347, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1-( Ethoxyacetyl) -2,5-1 dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -21methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned. Alternatively, cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid and diisobutyl cyclohexane-1,2-dicarboxylic acid, as disclosed in WO 2009/069483, are also preferred. Can be used. As an example of other cyclic succinate compounds, the compounds disclosed in WO 2009/057747 are also preferred.

Among the compounds of formula (I), if the group R ₃ to R ₆ is a hetero atom, it heteroatom is 16 atoms containing Group 15 atom or an oxygen and sulfur atom containing nitrogen and phosphorus atoms preferable. Examples of the compound in which the groups R _{3 to} R ₆ contain a Group 15 atom include compounds disclosed in JP-A-2005-306910. On the other hand, groups _R 3 to R ₆ are Examples of the compound containing a Group 16 atom include compounds disclosed in JP-2004-131537.

In addition, an internal electron donor compound that gives a molecular weight distribution equivalent to that of the succinate compound may be used. Examples of such a compound include a diphenyldicarboxylic acid ester described in JP2013-28704, a cyclohexenedicarboxylic acid ester described in JP2014-2016002, and a dicyclo described in JP2013-28705. Examples thereof include alkyldicarboxylic acid esters, diol dibenzoates described in Japanese Patent No. 4959920, and 1,2-phenylenedibenzoates described in WO 2010/078494.

1-2) Organoaluminium compound (component (ii))
Examples of the organoaluminum compound of the component (ii) include the following.
Trialkylaluminum such as triethylaluminum and tributylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide;

Partially halogenated alkylaluminum such as alkylaluminum dihalogenide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Partially hydrogenated alkylaluminum such as alkylaluminum dihydrides such as ethylaluminum dihydrides and propylaluminum dihydrides;
Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide, ethylaluminum ethoxybromid.

1-3) Electron donor compound (component (iii))
The electron donor compound of the component (iii) is generally referred to as an "external electron donor compound". As such a compound, an organosilicon compound is preferable. Preferred organosilicon compounds include:
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyldiethoxysilane, biso-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane Silane, Cyclohexylmethyldimethoxysilane, Cyclohexylmethyldiethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Methyltrimethoxysilane, n-propyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n-butyltriethoxysilane, iso- Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornantrimethoxysilane , 2-Norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyl Tetraethoxydisiloxane, methyl (3,3,3-trifluoro-n-propyl) dimethoxysilane, cyclohexylethyldimethoxysilane, cyclopentyl-t-butoxydimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyldimethoxysilane, n-propyltrimethoxy Silane, di-n-propyldimethoxysilane, texyltrimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t- Butyl-t-butoxydimethoxysilane, isobutyltrimethoxysilane, cyclohexylisobutyldimethoxysilane, di-sec-butyldimethoxysilane, isobutylmethyldimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, diethylaminotriethoxysilane, di Cyclopentyl-bis (ethylamino) silane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-Butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl (perhydroisoquinolin 2-) Il) dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropeniroxy) phenylsilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltri Butoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyl i-propyldimethoxysilane, cyclopentyl t-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyl i-butyldimethoxysilane, cyclopentyl i -Butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxylan, bisp-tolyl Dimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, diphenyldiethoxysilane, methyl (3,3,3-trifluoropropyl) Dimethoxysilane, ethyl silicate and the like are preferable.

1-4) Polymerization The raw material monomer is brought into contact with the catalyst prepared as described above to polymerize. At this time, it is preferable to first perform prepolymerization using the catalyst. The prepolymerization is a step of forming a polymer chain as a foothold for the subsequent main polymerization of the raw material monomer in the solid catalyst component. Prepolymerization can be carried out by a known method. Prepolymerization is usually carried out at 40 ° C. or lower, preferably 30 ° C. or lower, and more preferably 20 ° C. or lower. Next, the prepolymerized catalyst (prepolymerization catalyst) is introduced into the polymerization reaction system to carry out the main polymerization of the raw material monomer. The polymerization may be carried out in a liquid phase, a gas phase or a liquid-gas phase. The polymerization temperature is preferably room temperature to 150 ° C., more preferably 40 ° C. to 100 ° C. The polymerization pressure is preferably in the range of 3.3 to 6.0 MPa when carried out in the liquid phase, and preferably in the range of 0.5 to 3.0 MPa when carried out in the gas phase. Conventional molecular weight modifiers known in the art, such as chain transfer agents (eg, hydrogen or ZnEt _{2), may be used.}

Further, a polymerizer having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerizer, for example, one in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by vapor phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region consisting of an ascending tube, and a monomer is supplied and polymerized by a descending tube connected to the ascending tube. The polymer product is recovered while circulating. This method comprises means to prevent the gas mixture present in the ascending tube from entering the descending tube in whole or in part. Further, a gas or liquid mixture having a composition different from that of the gas mixture existing in the rising pipe is introduced into the falling pipe. As the above polymerization method, for example, the method described in JP-A-2002-520426 can be applied.

2) Ingredient (B)
The method for producing the component (B) is not limited. The component (B) may be produced by a known method using a known catalyst such as a Ziegler-Natta catalyst (also referred to as “ZN catalyst”) or a metallocene catalyst.

3) Method for Producing Polypropylene Composition The polypropylene composition of the present invention can be produced by mixing or melt-kneading the components (A) to (C) and, if necessary, other components. The method of mixing or kneading is not limited, but a method using a kneader such as an extruder is preferable. The conditions for kneading are not particularly limited, but the cylinder temperature is preferably 180 to 250 ° C. The polypropylene composition thus obtained is preferably in the form of pellets from the viewpoint of preventing classification of specific components and poor dispersion.

3. 3. Sheets and the like (1) Method for producing sheets and the like The sheets and the like of the present invention have at least one layer made of the above polypropylene composition. When the sheet or the like has a layer other than the polypropylene composition, the other layer is not particularly limited, but is a propylene homopolymer, a random copolymer, a block copolymer, or a polymer of any of these. Examples thereof include compositions containing a resin other than polypropylene as a main component.

The sheet or the like of the present invention can be produced by extrusion molding the polypropylene composition of the present invention. Alternatively, the sheet or the like of the present invention can be produced by dry-blending the components (A) to (C) and, if necessary, other components, and then extrusion-molding as it is. The molding temperature at this time may be as known, but the cylinder temperature is preferably 180 to 250 ° C. Further, the sheet or the like thus obtained can be subjected to secondary processing such as vacuum forming or biaxial stretching. The temperature in the secondary processing is also not limited, but is preferably 140 to 170 ° C.

(2) Characteristics of Sheets, etc. The sheets, etc. of the present invention have the characteristics of being excellent in transparency, rigidity, and impact resistance. The sheet or the like of the present invention preferably has a haze of 3.0% or less measured according to JIS K7136. Further, the sheet or the like of the present invention preferably has a taber stiffness (stiffness) of 1200 MPa or more measured according to JIS P8125.

(1) Ingredient (A)
The one manufactured as follows was used. The physical characteristics are shown in Table 1.
[Manufacturing Example A1]
The solid catalyst component (1) was prepared according to the preparation method described in Examples of JP-A-2011-500907. Specifically, it is as follows.
_{250 mL of TiCl 4} was introduced at 0 ° C. into a 500 mL four-necked round bottom flask purged with nitrogen. While stirring, according to the method described in Example 2 10.0g of the fine spherical _{MgCl 2 · 1.8C 2 H 5 OH} ( US Patent 4,399,054, however operating at 3000rpm instead of 10000rpm production And 9.1 mmol of diethyl-2,3- (diisopropyl) succinate were added. The temperature was raised to 100 ° C. and held for 120 minutes. The stirring was then stopped, the solid product was allowed to settle and the supernatant was sucked out. The following operation was then repeated twice: 250 mL of fresh TiCl ₄ was added, the mixture was reacted at 120 ° C. for 60 minutes and the supernatant was sucked out. The solid was washed 6 times with anhydrous hexane (6 x 100 mL) at 60 ° C. to give a solid catalyst (1).
The weight ratio of TEAL to the solid catalyst (1) of the solid catalyst (1) obtained above, triethylaluminum (TEAL), and diisopropyldimethoxysilane (DIPMS) is 11, and the weight ratio of TEAL / DIPMS is The contact was carried out at 12 ° C. for 24 minutes in an amount such that the amount was 3. The obtained catalyst system was prepolymerized by holding it in a suspended state in liquid propylene at 20 ° C. for 5 minutes to obtain a prepolymerized catalyst (S).
A prepolymerization catalyst (S) is introduced into the polymerization reactor to supply propylene as a monomer, and a small amount of ethylene and a molecular weight adjuster so that the ethylene concentration in the polymerization reactor is 0.118 mol% and the hydrogen concentration is 700 molppm. Supplyed hydrogen as. A propylene-ethylene copolymer was synthesized by adjusting the polymerization temperature to 70 ° C. and the polymerization pressure to 3.0 MPa. 0.2 parts by weight of an antioxidant (BASF B225) and 0.05 parts by weight of a neutralizing agent (calcium stearate) were added to 100 parts by weight of the obtained polymer, and the mixture was used in a Henschel mixer for 1 minute. Stirred and mixed. The mixture was melt-kneaded at a cylinder temperature of 230 ° C. using an NVC φ50 mm single-screw extruder manufactured by Nakatani Machinery Co., Ltd., and the extruded strands were cooled in water and then cut with a pelletizer to obtain a pellet-shaped polymer composition. .. The ethylene content of the polymer composition was 0.5% by weight, the MFR (temperature 230 ° C., load 2.16 kg) was 3.0 g / 10 minutes, and the polydisperse index (PI) was 5.8.

[Manufacturing Example A2]
A polymer composition was obtained in the same manner as in Production Example A1 except that the ethylene concentration in the polymerization reactor was 0.296 mol% and the hydrogen concentration was 770 molppm. The ethylene content of the polymer composition was 1.3% by weight, the MFR (temperature 230 ° C., load 2.16 kg) was 3.0 g / 10 minutes, and the polydisperse index (PI) was 5.8.

[Manufacturing example A3]
A polymer composition was obtained in the same manner as in Production Example A1 except that the hydrogen concentration in the polymerization reactor was set to 1050 molppm. The ethylene content of the polymer composition was 0.5% by weight, the MFR (temperature 230 ° C., load 2.16 kg) was 6.0 g / 10 minutes, and the polydisperse index (PI) was 6.0.

[Manufacturing example A4]
The solid catalyst component (2) was prepared by the method described in Example 1 of European Patent No. 674991. The solid catalyst is obtained by supporting Ti and diisobutyl phthalate as an internal donor on _{MgCl 2 by the method described in the above patent publication.}
The solid catalyst (2) obtained above and TEAL and cyclohexylmethyldimethoxysilane (CHMMS) were prepared in such an amount that the weight ratio of TEAL to the solid catalyst was 8 and the weight ratio of TEAL / CHMMS was 32. The contacts were contacted at −5 ° C. for 5 minutes. The obtained catalyst system was prepolymerized by holding it in a suspended state in liquid propylene at 20 ° C. for 5 minutes to obtain a prepolymerized catalyst (P1).
The prepolymerization catalyst (P1) was introduced into the polymerization reactor to supply propylene as a monomer and hydrogen as a molecular weight modifier so that the hydrogen concentration in the polymerization reactor was 410 molppm. A propylene polymer was synthesized by adjusting the polymerization temperature to 75 ° C. and the polymerization pressure to 3.0 MPa. The obtained homopolypropylene was melt-kneaded in the same manner as in Production Example A1 to obtain a polymer composition. The ethylene content of the polymer composition was 0% by weight, the MFR (temperature 230 ° C., load 2.16 kg) was 3.0 g / 10 minutes, and the polydisperse index (PI) was 4.2.

[Manufacturing Example A5]
The solid catalyst (2) used in Production Example A4, triethylaluminum (TEAL) as the organoaluminum compound, and dicyclopentyldimethoxysilane (DCPMS) as the external electron donor compound were used, and the weight ratio of TEAL to the solid catalyst was 20. Contact was carried out at 12 ° C. for 24 minutes in an amount such that the weight ratio of TEAL / DCPMS was 10. The obtained catalyst system was prepolymerized by holding it in a suspended state in liquid propylene at 20 ° C. for 5 minutes to obtain a prepolymerized catalyst (P2).
A two-stage polymerization method was carried out using two linked reactors using a prepolymerization catalyst (P2). A catalyst, propylene and hydrogen were supplied to the first-stage reactor, and propylene and hydrogen were supplied to the second-stage reactor to obtain a propylene polymer. The hydrogen concentration in the first stage was 180 molppm, the hydrogen concentration in the second stage was 7890 molppm, and the residence time was adjusted so that the ratio between the first stage and the second stage was 50:50. The polymerization temperature was 80 ° C. and the polymerization pressure was 4.4 MPa. The obtained homopolypropylene was melt-kneaded in the same manner as in Production Example A1 to obtain a polymer composition. The ethylene content of the polymer was 0% by weight, the MFR (temperature 230 ° C., load 2.16 kg) was 3.0 g / 10 minutes, and the polydisperse index (PI) was 5.8.

(2) Ingredient (B)
I used the following: The physical characteristics are shown in Table 2.
B1: ENGAGE8480 manufactured by Dow Chemical Co., Ltd.
B2: AFFINITY PL1850G manufactured by Dow Chemical Co., Ltd.
B3: ENGAGE8003 manufactured by Dow Chemical Co., Ltd.
B4: ENGAGE8402 manufactured by Dow Chemical Co., Ltd.
B5: Toughmer A-4090S manufactured by Mitsui Chemicals, Inc.

(3) Ingredient (C)
I used the following:
C1: Millad NX8000J manufactured by Milliken (nonitol-based nucleating agent)
C2: Millad 3988 manufactured by Milliken (sorbitol-based nucleating agent)
C3: ADEKA Corporation ADEKA STAB NA71 (phosphate ester-based nucleating agent)
C4: IRGACLEAR XT386 manufactured by BASF (triaminobenzene derivative-based nucleating agent)
However, from the viewpoint of preventing classification and poor dispersion of the crystal nucleating agent components, the crystal nucleating agent masterbatch was prepared and used as follows.
C1 Masterbatch: 80 parts by weight and 20 parts by weight of the matrix polymer for masterbatch produced as follows were mixed by stirring with a Henschel mixer for 1 minute. The mixture was melt-kneaded at a cylinder temperature of 230 ° C. using an NVC φ50 mm single-screw extruder manufactured by Nakatani Machinery Co., Ltd., and the extruded strands were cooled in water and then cut with a pelletizer to obtain a pellet-shaped C1 masterbatch composition. It was.
C2 masterbatch: In the same manner as in C1, 80 parts by weight of the matrix polymer for masterbatch and 20 parts by weight of C2 were mixed and melt-kneaded to obtain a C2 masterbatch composition.
C3 Masterbatch: Similar to C1 and C2 above, 80 parts by weight of the matrix polymer for masterbatch and 20 parts by weight of C3 were mixed and melt-kneaded to obtain a C3 masterbatch composition.
C4 masterbatch: 98 parts by weight of the matrix polymer for masterbatch and 2 parts by weight of C4 were mixed and melt-kneaded in the same manner as in C1 to C3 to obtain a C4 masterbatch composition.

[Manufacturing of matrix polymer for masterbatch]
The prepolymerization catalyst (P2) used in Production Example A5 was introduced into the polymerization reactor to supply propylene as a monomer and hydrogen as a molecular weight modifier so that the hydrogen concentration in the polymerization reactor was 2420 molppm. .. A propylene polymer was synthesized by adjusting the polymerization temperature to 80 ° C. and the polymerization pressure to 4.4 MPa. The obtained homopolypropylene was melt-kneaded in the same manner as in Production Example A1 to obtain a polymer composition. The ethylene content of the polymer composition (matrix polymer for masterbatch) is 0% by weight, MFR (temperature 230 ° C., load 2.16 kg) is 7.5 g / 10 minutes, and polydisperse index (PI) is 4.5. there were.

(4) Sheet molding A sheet molding machine having a thickness of 0.3 mm was obtained by molding at a molding temperature of 230 ° C. using a 25 mm φ3 type 3-layer film / sheet molding machine (manufactured by Thermo Plastic Industry Co., Ltd.).

(5) Evaluation method [Ethylene content in component (A)]
The sample was dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene, using a JEOL Ltd. JNM LA-400 (13C resonance frequency 100 ^MHz), measured by 13 C-NMR method.

[MFR]
According to JIS K7210-1, the component (A) was measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg. The component (B) was measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg.

[density]
The measurement was performed using a hydrometer (manufactured by Shinko Denshi Co., Ltd. (ViBRA DMA-220)) according to the underwater substitution method specified in JIS K7112.
[Multivariance Index (PI)]
The viscoelastic properties were measured by operating at a temperature of 190 ° C. using a UDS200 manufactured by ParPhysical Co., Ltd. at a frequency increasing from 0.1 rad / sec to 100 rad / sec. The value of the polydispersity index was obtained from the crossover elastic modulus using the following formula.
PI ⁼ 10 5 / Gc
In the formula, Gc is a crossover elastic modulus defined as an elastic modulus (unit: Pa) when G'(storage elastic modulus) = G "(loss elastic modulus).

[Transparency (haze)]
Using the original sheet as a test piece, the haze was measured by a haze measuring device (HM-150 type manufactured by Murakami Color Technology Laboratory Co., Ltd.) according to JIS K7136. The smaller the haze value, the better the transparency.

[Transparency after heating (haze)]
A 150 mm × 270 mm sheet material fixed to a metal frame was placed in an oven set at 210 ° C., heated for 30 seconds, then quickly taken out and allowed to cool to room temperature (23 ° C.). Using this as a test piece, the haze was measured by a haze measuring device (HM-150 type manufactured by Murakami Color Technology Laboratory Co., Ltd.) according to JIS K7136.

[Rigidity (stiffness)]
Using the original sheet as a test piece, in accordance with JIS P8125, using a Stiffness tester (TB-150) manufactured by Taber Co., Ltd. at a room temperature of 23 ° C., the Taber stiffness (stiffness) in the sheet pick-up direction (MD) and its vertical direction (TD). Was measured, and the average value was calculated. The larger the stiffness value, the better the rigidity.

[Impact resistance (surface impact strength)]
A 100 mm square test piece was cut out from the original sheet, and the surface impact strength was measured using a film impact tester (model 3J-30 + 100) manufactured by Toyo Seiki Seisakusho Co., Ltd. The conditions were as follows.
Uses a hemisphere with a tip shape of 1 inch. Pendulum energy: 3J
Clamp diameter: 50 mm
Atmospheric temperature: 0 ° C

[Secondary workability (drawdown time)]
A 150 mm × 270 mm sheet material fixed to a metal frame is placed in a test oven set at 210 ° C. (a temperature exceeding the equilibrium melting point of polypropylene of about 186 ° C. and near the preheating temperature in vacuum forming), and after melting. The draw-down property was evaluated by the time (t2-t1) from the time t1 when the seat was re-tensioned to the time t2 until the central portion of the seat hung down 1.5 cm due to its own weight. Drawdown causes uneven product wall thickness. The longer the drawdown time (t2-t1), the more difficult it is to draw down, so the secondary workability is excellent.

[Appearance of molded product (fish eye)]
The number of fish eyes (spherical defects having a diameter of 0.1 mm or more centered on an unmelted material or a gelled product) contained on the surface of the original sheet was visually observed and evaluated according to the following five criteria.
1: Very many fish eyes 2: Many fish eyes 3: Can see fish eyes 4: Fewer fish eyes 5: No fish eyes at all

[Example 1]
The ratio of polymer A1: polymer B1 is 98: 2 (% by weight), and the masterbatch is such that the crystal nucleating agent C1 is 0.4 parts by weight based on 100 parts by weight of the total of polymer A1 and polymer B1. 2 parts by weight of C1 was blended and dry blended. The dry blend was supplied to the above-mentioned film / sheet molding machine to obtain a sheet raw fabric having a thickness of 0.3 mm and evaluated.

[Examples 2 and 3]
Sheet raw fabrics were obtained and evaluated in the same manner as in Example 1 except that polymers A2 and A3 were used instead of the polymer A1.

[Example 4]
A sheet raw fabric was obtained and evaluated in the same manner as in Example 1 except that the compounding ratio of polymer A1: polymer B1 was changed to 92: 8 (% by weight).

[Example 5]
A sheet raw fabric was obtained and evaluated in the same manner as in Example 1 except that the polymer B2 was used instead of the polymer B1.

[Example 6]
A sheet raw fabric was obtained and evaluated in the same manner as in Example 1 except that the crystal nucleating agent C2 was used instead of the crystal nucleating agent C1.

[Example 7]
Same as in Example 1 except that 1.25 parts by weight of the C3 masterbatch was blended so that the crystal nucleating agent C1 was 0.25 parts by weight instead of 0.4 parts by weight of the crystal nucleating agent C1. Then, the sheet material was obtained and evaluated.

[Example 8]
Sheets in the same manner as in Example 1 except that 1 part by weight of C4 masterbatch was blended so that the crystal nucleating agent C1 was 0.02 parts by weight instead of 0.4 parts by weight of the crystal nucleating agent C1. The original fabric was obtained and evaluated.

[Example 9]
The composition used in Example 1 (MFR of A1 = 3.0 g / 10 minutes) is on the surface layer, and the composition used in Example 3 (MFR of A3 = 6.0 g / 10 minutes) is on the intermediate layer. Then, these were coextruded to produce an unstretched sheet having a layer ratio of 1: 5: 1 and having a thickness of 0.3 mm in two types and three layers, and evaluated. Practically, in consideration of in-process recycling using sheet scraps as recycled materials, a material having a high MFR was used for the intermediate layer in this example.

[Example 10]
A sheet raw material was obtained and evaluated in the same manner as in Example 1 except that the polymer A5 containing no ethylene component was used instead of the polymer A1.

[Comparative Example 1]
A sheet raw fabric was obtained and evaluated in the same manner as in Example 1 except that the polymer A4 having a small polydispersity index was used instead of the polymer A1.

[Comparative Example 2]
A sheet raw fabric was obtained and evaluated in the same manner as in Example 1 except that the compounding ratio of polymer A1: polymer B1 was changed to 99.7: 0.3 (% by weight).

[Comparative Example 3]
A sheet raw fabric was obtained and evaluated in the same manner as in Example 1 except that the polymer B3 having a low density was used instead of the polymer B1.

[Comparative Example 4]
A sheet raw fabric was obtained and evaluated in the same manner as in Example 1 except that the polymer B4 having a large MFR was used instead of the polymer B1.

[Comparative Example 5]
Instead of blending 2% by weight of polymer B1, 3% by weight of polymer B5, which is a copolymer of ethylene and α-olefin having 4 carbon atoms, was blended in the same manner as in Example 1. And evaluated.

[Comparative Example 6]
Same as in Example 8 except that the blending amount of the crystal nucleating agent C4 was changed from 0.02 parts by weight to 0.01 parts by weight and the blending amount of the C4 masterbatch was changed to 0.5 parts by weight. Then, the sheet material was obtained and evaluated.

The evaluation results are shown in Table 3. It is clear that the sheets obtained using the compositions of the present invention are excellent in transparency, rigidity, and impact resistance. Furthermore, it is clear that the sheet has good secondary workability and appearance.

Claims (6)

A propylene (co) polymer containing 0 to 2% by weight of ethylene as the component (A),
The component (B) contains a copolymer of ethylene and an α-olefin having 8 or more carbon atoms, and the component (C) contains a crystal nucleating agent.
The MFR (230 ° C., 2.16 kg) of the component (A) is 0.3 to 10 g / 10 minutes, and the polydisperse index is 5 to 10.
The density of the copolymer of the component (B) is 0.890 to 0.915 g / cm ³ , and the MFR (190 ° C., 2.16 kg) is 0.5 to 5 g / 10 minutes.
The weight ratio of component (A): component (B) is 90 to 99.5: 0.5 to 10.
A total of 100 parts by weight of the component (A) and the component (B) contains 0.015 to 0.5 parts by weight of the component (C).
Polypropylene composition. The corresponding monomer is polymerized using a solid catalyst in which the component (A) contains an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component, and a catalyst containing an organoaluminum compound. The composition according to claim 1, which is a propylene (co) polymer thus obtained. The composition according to claim 1 or 2, wherein the α-olefin in the component (B) has 8 carbon atoms. The composition according to any one of claims 1 to 3, wherein the ethylene content in the component (A) is 0.3 to 2% by weight. The composition according to any one of claims 1 to 4, wherein the MFR (230 ° C., 2.16 kg) of the component (A) is 2 to 7 g / 10 minutes. A sheet or film produced from the composition according to any one of claims 1-5.