JP2010159320A - Polypropylene sheet and formed body obtained from the same - Google Patents

Abstract

Disclosed is a polypropylene sheet that is excellent in transparency and has a small decrease in transparency with time, and a molded body obtained from the sheet.
A polypropylene sheet is obtained by using a metallocene catalyst, and a polypropylene homopolymer (A) satisfying the following requirements (1) to (4) is melt-extruded at a resin temperature of 180 ° C. or more to obtain a molten sheet: It is a sheet having a film thickness of 0.1 to 1.0 mm obtained by cooling at a cooling rate of 50 to 100 ° C./second, and HAZE (HAZE (t)) converted to a thickness of 1 mm is 40% or less. A polypropylene sheet having an increase in HAZE of 1.5 or less when the sheet is held at 40 ° C. for 8 days;
(1) MFR is 0.1 to 10 g / 10 min. (2) Melting point measured by DSC is 145 to 165 ° C.
(3) Mw / Mn measured by GPC is 2 to 3.5
(4) Elution integral up to 90 ° C measured by CFC is 4% or less [Selection figure] None

Description

  The present invention relates to a polypropylene sheet that is excellent in transparency and has a small decrease in transparency with time, and a molded body obtained from the sheet.

Polypropylene is used as a sheet or a sheet forming container as a material excellent in impact resistance, hygiene, and environmental compatibility.
However, polypropylene has a problem that its transparency is inferior to that of resins such as polystyrene resin and polyvinyl chloride resin.

  As a method for improving the transparency of polypropylene, a method of copolymerizing other olefins, a method of adding a crystal nucleating agent, and a combination thereof have been proposed. However, the former method may impair the rigidity and heat resistance of the sheet, and the latter method may cause a problem of smoke generation at the time of sheet forming, and these sheets may be used for vacuum forming, vacuum pressure forming, etc. When it is molded by thermoforming, transparency and transparency may be extremely impaired.

Other methods for improving the transparency of the polypropylene sheet include (1) a weight average molecular weight of 30,000 to 1,000,000, (2) an isotactic pentad fraction of 0.900 to 0.949, (3) Heterogeneous bonds resulting from 2,1-insertion reaction and 1,3-insertion reaction are 0
To 1 mol%, (4) Mw / Mn from 1.5 to 3.8, and (5) elution of polypropylene into orthodichlorobenzene by raising the temperature of orthodichlorobenzene continuously or stepwise. When the amount of the component is measured, the position of the main elution peak is 95 ° C. or higher, and the amount of the component eluted in the temperature range of ± 10 ° C. centering on the main elution peak is eluted at a temperature higher than 0 ° C. A method using polypropylene that is 90% or more of the total amount of eluted components has been proposed (Patent Document 1). However, in the invention described in this document, a decrease in transparency of the sheet with time is not studied.
JP 2000-230086

  The present invention has been made under the circumstances as described above. That is, an object of the present invention is to provide a polypropylene sheet that is excellent in transparency and has a low transparency deterioration rate with time, and a molded product obtained from this sheet.

The polypropylene sheet according to the present invention is obtained using a metallocene catalyst, and a polypropylene homopolymer (A) satisfying the following requirements (1) to (4) is melt-extruded at a resin temperature of 180 ° C. or more to form a molten sheet: A sheet having a film thickness of 0.1 to 1.0 mm obtained by cooling at a cooling rate of 50 to 100 ° C./second, and has a HAZE (HAZE (t)) of 40% / mm or less per unit thickness. The increase rate of HAZE when the sheet is held at 40 ° C. for 8 days is 1.5 or less.
(1) Melt flow rate (MFR) is in the range of 0.1 to 10 g / 10 minutes (2) Melting point measured by differential scanning calorimeter (DSC) is 145 to 165 ° C. (3) Gel The molecular weight distribution index (Mw / Mn) measured by permeation chromatography (GPC) is 2 to 3.5. (4) The elution integrated amount up to 90 ° C. measured by the cross fractionation chromatography (CFC) 4% or less.

The metallocene catalyst is preferably a catalyst containing a metallocene compound represented by the following general formula [III].

（式中、Ｍは第４族遷移金属であり、Ｒ¹およびＲ³は水素原子であり、Ｒ²およびＲ⁴は炭素数１〜５の直鎖状または分岐状アルキル基であり、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、
Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は水素原子、炭化水素基、ケイ素含有基から選ばれ（但し、Ｒ⁶、Ｒ⁷、Ｒ¹⁰およびＲ¹¹は同時に水素原子ではない）、それぞれ同一でも異なっていてもよく、また、Ｒ⁵からＲ¹²の隣接した置換基は互いに結合して環を形成してもよく、Ｙ
は第１４族元素であり、Ｒ¹³、Ｒ¹⁴は相互に同一でも異なっていてもよく、互いに結合して環を形成してもよい炭素原子数１〜２０の炭化水素基であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれ、ｊは１〜４の整数であり、ｊが２以上の時は、Ｑは互いに同一でも異なっていてもよい。）
本発明に係るトレイ、カップ等の成形体は、前記ポリプロピレンシートを熱成形して得られる。

(In the formula, M is a Group 4 transition metal, R ¹ and R ³ are hydrogen atoms, R ² and R ⁴ are linear or branched alkyl groups having 1 to 5 carbon atoms, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group (provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms at the same time), and each may be the same The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring;
Is a Group 14 element, R ¹³ and R ¹⁴ may be the same or different from each other, and are hydrocarbon groups of 1 to 20 carbon atoms that may be bonded to each other to form a ring, and Q is A halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand that can be coordinated by a lone electron pair is selected in the same or different combination, j is an integer of 1 to 4, and when j is 2 or more , Q may be the same as or different from each other. )
Formed bodies such as trays and cups according to the present invention are obtained by thermoforming the polypropylene sheet.

  The polypropylene sheet of the present invention and the molded product obtained from this sheet are excellent in transparency and have a small decrease in transparency over time.

Hereinafter, the polypropylene sheet according to the present invention and a molded article obtained from the sheet will be specifically described.
The polypropylene sheet according to the present invention is obtained by using a metallocene catalyst, and after forming a polypropylene homopolymer (A) satisfying the following requirements (1) to (4) into a sheet, the polypropylene sheet is cooled at an average cooling rate of 50 ° C./second. HAZE when the sheet has a thickness of 0.1 to 1.0 mm, the HAZE per unit thickness (HAZE (t)) is 40% / mm or less, and the sheet is held at 40 ° C. for 8 days. The increase rate is 1.5 or less.
(1) Melt flow rate (MFR) is in the range of 0.1 to 10 g / 10 minutes (2) Melting point measured by differential scanning calorimeter (DSC) is 145 to 165 ° C. (3) Gel The molecular weight distribution index (Mw / Mn) measured by permeation chromatography (GPC) is 2 to 3.5. (4) The elution integrated amount up to 90 ° C. measured by the cross fractionation chromatography (CFC) 4% or less.

<< Requirement (1) >>
The polypropylene homopolymer (A) used in the present invention has an MFR in the range of 0.1 to 10 g / 10 minutes, preferably 0.1 to 5 g / 10 minutes. The MFR can be adjusted by changing the polymerization temperature or using hydrogen as a chain transfer agent.
When the MFR of the polypropylene homopolymer (A) is in the above range, the sheet is excellent in high-speed moldability.

<< Requirement (2) >>
The polypropylene homopolymer (A) used in the present invention has a melting point measured by DSC of 145 to 165 ° C, preferably 155 to 165 ° C. By using a metallocene catalyst system described later as the catalyst, a polymer having a melting point within the above range can be obtained. Moreover, the polymer from which melting | fusing point differs can be manufactured by changing the metallocene compound to be used.
When the melting point measured by DSC of the polypropylene homopolymer (A) is in the above range, the obtained polypropylene sheet and the molded product obtained from this sheet are excellent in heat resistance.

<< Requirement (3) >>
The polypropylene homopolymer (A) used in the present invention has a molecular weight distribution index (Mw / Mn) measured by GPC in the range of 2 to 3.5, preferably 2 to 3. By using a metallocene catalyst system described later as a catalyst, a polymer having Mw / Mn within the above range can be obtained. Moreover, the polymer from which Mw / Mn differs can be manufactured by changing the metallocene compound to be used.

  When the Mw / Mn of the polypropylene homopolymer (A) is in the above range, there are few bleedouts due to the small amount of low molecular weight components, and the resulting polypropylene sheet and the molded product obtained from this sheet are excellent in transparency and transparent over time. There is little decline in sex.

<< Requirement (4) >>
The polypropylene homopolymer (A) used in the present invention has an elution integral amount up to 90 ° C. measured by the CFC method of 4% or less, preferably 2% or less, more preferably 1% or less. By using a metallocene catalyst system, which will be described later, as a catalyst, a polymer having an integrated elution amount in the above range can be obtained. Moreover, the polymer from which an elution integral amount differs can be manufactured by changing the metallocene compound to be used.

In the CFC method of polypropylene homopolymer (A), when the integrated amount of elution up to 90 ° C. is in the above range, the low molecular weight component is small, so there is little bleed out, and the resulting polypropylene sheet and the molded product obtained from this sheet are transparent Excellent in transparency and little decrease in transparency over time.
The polypropylene homopolymer (A) used in the present invention preferably satisfies at least one of the following requirements (5) to (7) in addition to the requirements (1) to (4).

<< Requirement (5) >>
The polypropylene homopolymer (A) used in the present invention has a mesotriad fraction measured by ¹³ C-NMR in the range of 97.0 to 99.9%, preferably 97.5 to 99.5%. The mesotriad fraction (mm fraction) indicates the proportion of isotactic chains existing in triad units in the molecular chain, and the propylene monomer at the center of the chain in which three propylene monomer units are continuously meso-bonded Unit fraction.

By using a metallocene catalyst system, which will be described later, as the catalyst, a polymer having a mesotriad fraction in the above range can be obtained. In addition, the mesotriad fraction can be adjusted by changing the polymerization temperature.
When the mesotriad fraction of the polypropylene homopolymer (A) is in the above range, the obtained polypropylene sheet and the molded product obtained from this sheet are excellent in heat resistance.

<< Requirement (6) >>
The polypropylene homopolymer (A) used in the present invention has a mesopentad fraction measured by ¹³ C-NMR in the range of 94.0 to 99.9%, preferably 95.0 to 99.5%. . The mesopentad fraction (mmmm fraction) indicates the proportion of isotactic chains existing in pentad units in the molecular chain, and the propylene monomer units in the center of a chain in which five propylene monomer units are continuously meso-bonded. Is a fraction of.

By using a metallocene catalyst system, which will be described later, as a catalyst, a polymer having a pendart fraction within the above range can be obtained. In addition, the pendart fraction can be adjusted by changing the polymerization temperature.
When the Pendat fraction of the polypropylene homopolymer (A) is in the above range, the resulting polypropylene sheet and the molded product obtained from this sheet are excellent in heat resistance.

<< Requirement (7) >>
The polypropylene homopolymer (A) used in the present invention is obtained from the ¹³ C-NMR spectrum, in the proportion of heterogeneous bonds based on 2,1-insertion of propylene monomer in all propylene structural units and 1,3-insertion. The sum of the proportions of the heterogeneous bonds based is 0.1 mol% or less, preferably 0.05 mol% or less. By using a metallocene catalyst system, which will be described later, as a catalyst, it is possible to obtain a polymer in which the sum of the proportions of heterogeneous bonds is within the above range. Moreover, the sum value of the proportions of heterogeneous bonds can be adjusted by changing the polymerization temperature.

  When the sum of the proportion of heterogeneous bonds based on 2,1-insertion and the proportion of heterogeneous bonds based on 1,3-insertion in the polypropylene homopolymer (A) is within the above range, the resulting polypropylene sheet and obtained from this sheet The molded body is excellent in heat resistance.

The measuring method of each physical property will be described later.
By using the polypropylene homopolymer (A) as a material for the polypropylene sheet, it is possible to obtain a polypropylene sheet that is excellent in transparency and has a small decrease in transparency with time and a molded article obtained from this sheet.

(Method for producing polypropylene homopolymer (A))
Hereinafter, the manufacturing method of a polypropylene homopolymer (A) is demonstrated.
In the method for producing the polypropylene homopolymer (A) used in the present invention, the polypropylene homopolymer (A) is the requirements (1) to (4), preferably the requirements (5) and / or (6). However, it is usually produced by homopolymerizing propylene in the presence of a polymerization catalyst containing a metallocene compound having a cyclopentadienyl skeleton in the molecule.

  The metallocene compound having a ligand having a cyclopentadienyl skeleton in the molecule is represented by a non-bridged metallocene compound represented by the following general formula [I] and the following general formula [II] from its chemical structure. Two types of bridged metallocene compounds can be exemplified. Among these, a bridged metallocene compound represented by the general formula [II] is preferable.

前記一般式［Ｉ］および［II］において、Ｍはチタン原子、ジルコニウム原子またはハフニウム原子を示し、
Ｑはハロゲン原子、炭化水素基、アニオン配位子、および孤立電子対で配位可能な中性配位子から選ばれ、
ｊは１〜４の整数であり、
Ｃｐ¹およびＣｐ²は、互いに同一か又は異なっていてもよく、Ｍと共にサンドイッチ構造を形成することができるシクロペンタジエニル基または置換シクロペンタジエニル基である。ここで、置換シクロペンタジエニル基は、インデニル基、フルオレニル基、アズレニル基およびこれらが一つ以上の炭化水素基で置換された基も包含し、インデニル基、フルオレニル基、アズレニル基の場合はシクロペンタジエニル基に縮合する不飽和環の二重結合の一部ないし全部は水添されていてもよい。

In the general formulas [I] and [II], M represents a titanium atom, a zirconium atom or a hafnium atom,
Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair of electrons,
j is an integer of 1 to 4,
Cp ¹ and Cp ² may be the same or different from each other, and are a cyclopentadienyl group or a substituted cyclopentadienyl group that can form a sandwich structure with M. Here, the substituted cyclopentadienyl group includes an indenyl group, a fluorenyl group, an azulenyl group, and a group in which these are substituted with one or more hydrocarbon groups, and in the case of an indenyl group, a fluorenyl group, an azulenyl group, Some or all of the double bonds of the unsaturated ring condensed to the pentadienyl group may be hydrogenated.

In the general formula [II], Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or divalent germanium. -Containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO _2- , -Ge-, -Sn-, -NR ^a- , -P (R ^a ) -, - P (O) ( R a) -, - BR a - or -AlR ^a - it shows the. (However, ^Ra is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen atom and a hydrocarbon group having 1 to 20 carbon atoms. Is a nitrogen compound residue bonded with one or two.)

Polymerization catalysts preferably used in the present invention include bridged metallocene compounds represented by the following general formula [III] disclosed in International Publication (WO01 / 27124) filed by the present applicant, and organometallics It is a metallocene catalyst comprising at least one compound selected from compounds capable of reacting with a compound, an organoaluminum oxy compound and a metallocene compound to form an ion pair, and optionally a particulate carrier.

前記一般式［III］において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は水素原子、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 [III], 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 and R ¹⁴ are It is selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and each may be the same or different.

Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, linear hydrocarbon group such as n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl- Branched hydrocarbon groups such as 1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, Cyclic saturated hydrocarbon groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group, etc. Unsaturated hydrocarbon group; saturated hydrocarbon group substituted with cyclic unsaturated hydrocarbon group such as benzyl group, cumyl group, 1,1-diphenylethyl group, triphenylmethyl group; methoxy group, ethoxy group, phenoxy group And a heteroatom-containing hydrocarbon group such as a furyl group, an N-methylamino group, an N, N-dimethylamino group, an N-phenylamino group, a pyryl group, and a 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. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [III], R ¹ , R ² , R ³ and R ⁴ substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² And R ⁴ are more preferably a hydrocarbon group having 1 to 20 carbon atoms, R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are linear or branched having 1 to 5 carbon atoms. Particularly preferred is an alkyl group.

In the general formula [III], R ⁵ to R ¹² substituted on the fluorenyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-described hydrocarbon groups. The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. A preferred embodiment is a fluorenyl ring in which R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not simultaneously hydrogen atoms.

In the general formula [III], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a Group 14 element, more preferably carbon, silicon, or germanium, and more preferably a carbon atom.

R ¹³ and R ¹⁴ substituted on Y may be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms which may be bonded to each other to form a ring, preferably a carbon atom It is selected from an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 20 carbon atoms. As such a substituent, a methyl group, an ethyl group, a phenyl group, a tolyl group and the like are preferable. R ¹³ and R ¹⁴ are R ⁵ to R ¹² optional substituents (usually R ⁵ or R ¹² ) or R ¹ to R ⁴ optional substituents (provided that R ¹ is usually R ^1). Or R ⁴ ) may be bonded to each other to form a ring.

In the general formula [III], M is preferably a Group 4 transition metal, more preferably a titanium atom, a zirconium atom, or a hafnium atom.
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 a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and specific examples of the hydrocarbon group include the same as 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, and 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 the preferable bridged metallocene compound include dimethylmethylene (3-tert-butyl-
5-Methylcyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, 1-phenylethylidene (4-tert-butyl-2-methylcyclopentadienyl) (octamethyloctahydrodibenzofur Oleenyl) zirconium dichloride, [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 and the like.

In the metallocene catalyst used for the production of the polypropylene homopolymer (A), ions react with the organometallic compound, organoaluminum oxy compound, and metallocene compound used together with the metallocene compound represented by the general formula [III]. Regarding at least one compound (cocatalyst) selected from the compounds forming a pair, and the particulate carrier used as necessary, the above-mentioned publications (WO01 / 27124) and JP-A-11-315109 by the applicant of the present application. The compounds disclosed in the publication can be used without limitation.

  The polypropylene homopolymer (A) uses a polymerization apparatus in which one reactor or one or more reactors are connected in series, and in the presence of the metallocene catalyst, for example, a polymerization temperature of 0 to 100 ° C., a polymerization pressure of normal pressure to It can be produced by polymerizing propylene under polymerization conditions of 5 MPa gauge pressure.

(Elastomer (B))
In the present invention, it is preferable to use the polypropylene homopolymer (A) as a plain polypropylene sheet and molded article, but the elastomer (B) is added for the purpose of imparting characteristics such as impact resistance and flexibility. can do.

The elastomer (B) is an ethylene / α-olefin random copolymer (Ba).
, Ethylene / α-olefin / non-conjugated polyene random copolymer (Bb), hydrogenated block copolymer (Bc), propylene / α-olefin copolymer (Bd), other elastic polymers , And mixtures thereof.

Examples of the ethylene / α-olefin random copolymer rubber (Ba) include a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. In the ethylene / α-olefin random copolymer rubber (Ba), the molar ratio between the structural unit derived from ethylene and the structural unit derived from α-olefin (structural unit derived from ethylene / α- The structural unit derived from olefin) is usually 95/5 to 15/85, preferably 80/20 to 25/75.

Further, the ethylene / α-olefin random copolymer (Ba) was 230 ° C.,
The MFR measured at a load of 2.16 kg is usually 0.1 g / 10 min or more, preferably 0.5 to 30 g / 10 min.

The ethylene / α-olefin / non-conjugated polyene random copolymer (Bb) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. Examples of the α-olefin having 3 to 20 carbon atoms are the same as those described above.

As non-conjugated polyethylene, 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene Acyclic dienes such as norbornadiene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1, 5-heptadiene, 6-methyl-1,
Examples include chain non-conjugated dienes such as 7-octadiene and 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene. Of these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used.

In the ethylene / α-olefin / non-conjugated polyene random copolymer (Bb), the constitutional unit derived from ethylene is usually 94.9 to 0.1 mol%, preferably 89.5 to 40 mol%. Yes, the structural unit derived from α-olefin is usually 5 to 45 mol%, preferably 10 to 40 mol%, the structural unit derived from non-conjugated polyene is usually 0.1 to 25 mol%, Preferably it is 0.5-20 mol%. However, in the present invention, the total of the structural unit derived from ethylene, the structural unit derived from α-olefin, and the structural unit derived from non-conjugated polyene is 100 mol%. MF of ethylene / α-olefin / non-conjugated polyene random copolymer (Bb) measured at 230 ° C. under a load of 2.16 kg
R is usually in the range of 0.05 g / 10 min or more, preferably 0.1 to 30 g / 10 min.

Specific examples of the ethylene / α-olefin / non-conjugated polyene random copolymer (Bb) include an ethylene / propylene / diene terpolymer (EPDM).
The hydrogenated block copolymer (Bc) is a hydrogenated block copolymer having a block form represented by the following formula (a) or (b), and the hydrogenation rate is usually 90 mol%. More preferably, the hydrogenated block copolymer is 95 mol% or more.
X (YX) _n (a)
(YX) _n (b)

Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymerization block represented by X in the formula (a) or the formula (b) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and lower alkyl-substituted styrene. And styrene such as vinyl naphthalene or derivatives thereof. These can be used individually by 1 type, and can also be used in combination of 2 or more type. Examples of the conjugated diene constituting the polymer block represented by Y in the formula (a) or (b) include butadiene, isoprene, chloroprene and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more type. n is usually an integer of 1 to 5, preferably 1 or 2.

Specific examples of the hydrogenated block copolymer (Bc) include styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / ethylene / propylene / styrene block copolymer (SEPS), and styrene. -Styrene-type block copolymers, such as ethylene propylene block copolymer (SEP), etc. are mentioned. The block copolymer before hydrogenation can be produced, for example, by a method in which block copolymerization is performed in an inert solvent in the presence of a lithium catalyst or a Ziegler catalyst. A detailed manufacturing method is described in, for example, Japanese Patent Publication No. 40-23798.

The hydrogenation treatment can be performed in an inert solvent in the presence of a known hydrogenation catalyst. Detailed methods are described in, for example, Japanese Patent Publication Nos. 42-8704, 43-6636, and 46-20814. When butadiene is used as the conjugated diene monomer, the ratio of the 1,2-bond amount in the polybutadiene block is usually 20 to 80% by mass, preferably 30 to 60% by mass. A commercial item can also be used as a hydrogenated block copolymer (Bc). Specifically, Clayton G1657 (registered trademark)
(Manufactured by Shell Chemical Co., Ltd.), Septon 2004 (registered trademark) (manufactured by Kuraray Co., Ltd.), Tuftec H1052
(Registered trademark) (manufactured by Asahi Kasei Co., Ltd.).

Propylene / α-olefin copolymer rubber (Bd) is composed of propylene and 4 to 20 carbon atoms.
It is a random copolymer rubber with an α-olefin. In the propylene / α-olefin random copolymer (Bd), the molar ratio of the structural unit derived from propylene to the structural unit derived from α-olefin (the structural unit derived from propylene / α-olefin) The structural unit derived from is usually 95/5 to 5/95, preferably 80/15 to 20/80. In the propylene / α-olefin random copolymer rubber (Bd), two or more α-olefins may be used, one of which may be ethylene. Propylene / α-olefin random copolymer rubber (Bd) has an MFR measured at 230 ° C. and a load of 2.16 kg is usually 0.1 g / 10 min or more, preferably 0.5-30 g / 10 min. Is in.

An elastomer (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
In this invention, the said elastomer (B) is 0-50 mass parts normally with respect to 100 mass parts of polypropylene homopolymers (A), Preferably it is used in the quantity within the range of 1-20 mass parts.

(Polyethylene resin (C))
For the purpose of imparting functions such as impact resistance and dimensional stability, the polypropylene sheet of the present invention and the molded body obtained from this sheet are used together with the elastomer (B) or in place of the elastomer (B) with a polyethylene resin (C ) May be added.

For example, when imparting impact resistance while suppressing a decrease in transparency, a density of 0.900 to 0 produced by copolymerizing ethylene and an α-olefin having 4 or more carbon atoms in the presence of a metallocene catalyst. It is preferred to add 930 kg / m ³ linear low density polyethylene.

As another example, when improving moldability, it is desirable to add high-pressure polyethylene. Here, the high-pressure polyethylene is a polyethylene having a long chain branch obtained by radical polymerization of ethylene in the presence of peroxide at a pressure of 100 kg / cm ² or more. Preferred melt flow rate of high pressure polyethylene (ASTM
D1238, measured at 190 ° C. and a load of 2.16 kg) is usually in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 10 g / 10 min. The density (ASTM D1505) is usually 0.900 to 0.940 g / cm ³ , preferably 0.910 to 0.930 g / cm ³ .
It is in the range of cm ³ .

  The content of the polyethylene resin (C) in the propylene-based resin composition containing the polypropylene homopolymer (A) and the polyethylene resin (C) varies depending on the properties to be imparted, but is usually 0 to 30% by mass, preferably 1 to 20% by mass. Polyethylene resin (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  In the case of a propylene-based resin composition comprising a polypropylene homopolymer (A), an elastomer (B) and a polyethylene resin (C), the amount of the polypropylene homopolymer (A) varies depending on the properties to be imparted, Usually, it is in the range of 70 to 99% by mass, preferably 80 to 97% by mass. Moreover, the total amount of an elastomer (B) and a polyethylene resin (C) is 0-30 mass parts normally with respect to 100 mass parts of polypropylene homopolymers (A), Preferably it is 1-20 mass parts. In addition, the ratio of an elastomer and polyethylene can be arbitrarily adjusted according to the objective.

(Nucleating agent (D))
A nucleating agent (D) may be added to the polypropylene homopolymer (A) as necessary to improve transparency and heat resistance.

  Examples of the nucleating agent (D) used in the present invention include sorbitol compounds such as dibenzylidene sorbitol, organophosphate compounds, rosinate compounds, C4-C12 aliphatic dicarboxylic acids and metal salts thereof. be able to.

  Of these, organophosphate compounds are preferred. The organic phosphate ester compound is a compound represented by the following general formula [d-1] and / or [d-2].

前記の式［d-1］、［d-2］中、Ｒ¹は、炭素原子数１〜１０の２価炭化水素基であり、
Ｒ²およびＲ³は、水素または炭素原子数１〜１０の炭化水素基であって、Ｒ²とＲ³は同じであっても異なっていてもよく、Ｍは、１〜３価の金属原子であり、ｎは１〜３の整数であり、ｍは１または２である。

In the above formulas [d-1] and [d-2], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ may be the same or different, and M is a 1-3 valent metal atom N is an integer of 1 to 3, and m is 1 or 2.

Specific examples of the organic phosphate compound represented by the general formula [d-1] include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium- 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium- 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene
-Bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2 ' -Methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene -
Bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t -Octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium -Bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) ) Phosphate], sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butyl) Phenyl) phosphate, sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylpheny) ) Phosphate, sodium-2,2′-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-methylene-bis (4,6-di-ethylphenyl) phosphate, Potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [
2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] , Barium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t- Butyl fell) phosphate], aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and the like. These can be used in a mixture of two or more.

An organophosphate compound that can also be used as a hydroxyaluminum phosphate compound represented by the general formula [d-2], in particular, R ² and R ³ are both tert-butyl groups.
A compound represented by the general formula [d-3] is preferable.

式［d-3］において、Ｒ¹は、炭素原子数１〜１０の２価炭化水素基であり、ｍは１または２である。特に好ましい有機リン酸エステル系化合物は、一般式［d-4］で表される化
合物である。

In the formula [d-3], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, m is 1 or 2. A particularly preferred organophosphate compound is a compound represented by the general formula [d-4].

式［d-4］において、Ｒ¹は、メチレン基またはエチリデン基である。
式［d-4］で表される化合物として具体的には、ヒドロキシアルミニウム-ビス［２,２-メチレン-ビス（４,６-ジ-t-ブチル）フォスフェート］、ヒドロキシアルミニウム-ビス
［２,２-エチリデン-ビス（４,６-ジ-t-ブチル）フォスフェート］が挙げられる。

In the formula [d-4], R ¹ represents a methylene group or an ethylidene group.
Specific examples of the compound represented by the formula [d-4] include hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate], hydroxyaluminum-bis [2 , 2-ethylidene-bis (4,6-di-t-butyl) phosphate].

Specific examples of the sorbitol compound include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, and 1,3-benzylidene-2,4- p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,
4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol,
1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) Sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (Pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 3-p-
Chlorbenzylidene-2,4-benzylidenesorbitol, 1,3-p-chlorobenzylidene-
2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1, Examples thereof include 3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol or 1,3,2,4-di (p-chlorobenzylidene) sorbitol. In particular, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol or 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol preferable.

Specific examples of C4-C12 aliphatic dicarboxylic acids and metal salts thereof that can be used in the present invention include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and their Li, Na, Mg, Ca, Ba, Al salt, etc. can be mentioned. In addition, aromatic carboxylic acids and metal salts thereof that can be used as the nucleating agent (D) in the present invention include benzoic acid, allyl-substituted acetic acid, aromatic dicarboxylic acids, and Group 1 to 3 metal salts of these periodic tables. Yes, specifically, benzoic acid, p-isopropylbenzoic acid, o-tertiary butyl benzoic acid, p-tertiary butyl benzoic acid, monophenylacetic acid, diphenylacetic acid, phenyldimethylacetic acid, phthalic acid, and these Li, Na, Mg, Ca, Ba, Al salt, etc. can be mentioned.

The nucleating agent (D) used in the present invention is 0.05 to 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight, based on 100 parts by weight of the polypropylene homopolymer (A). It is desirable to add in. A polypropylene sheet made of a polypropylene homopolymer containing the nucleating agent (D) in the above proportion and a molded product obtained from this sheet have excellent transparency. In addition, when the compounding quantity of a nucleating agent (D) becomes more than the said range, a film thickness precision may fall.

(Other ingredients)
The polypropylene sheet of the present invention and the molded product obtained from this sheet are, as necessary, vitamins, antioxidants, heat stabilizers, weathering stabilizers, lubricants, antiblocking agents as long as the object of the present invention is not impaired. In addition, additives such as mineral oil may be included.

(Sheet)
As a method for producing the polypropylene sheet of the present invention, an extrusion method using a commonly used T die, an inflation method, or the like can be used.

  A specific production example will be described by an extrusion method using a T-die. A polypropylene homopolymer (A) and an additive that is added as necessary are put into an extruder, and the temperature is 180 to 260 ° C. After heat-melting and kneading, the sheet is extruded from a die lip of a T die, the molten sheet is cooled, and is taken up by a take-up machine such as a nip roll to produce a sheet. As a cooling method of the molten sheet, a roll cooling method using an air knife method or an air chamber method and a cooling method using air cooling, a narrowing cooling method using a polishing roll method, a swing roll method, a belt cast method, a contact cooling method using a coolant such as a water cooling method, etc. Etc. can be adopted.

  The molten sheet is preferably cooled at a cooling rate of 50 to 100 ° C./second. Here, the cooling rate refers to a value calculated from the time required for cooling from the resin temperature at the die outlet to 100 ° C. near the crystallization temperature. Although the temperature at the time of extrusion melting varies depending on the characteristics of the resin, it is usually selected within the range of 180 to 260 ° C, preferably 200 to 260 ° C. Using the polypropylene homopolymer (A), a sheet having high transparency and little change with time in transparency can be produced by rapidly cooling the molten sheet in the solidification stage in sheet molding.

  The polypropylene sheet of the present invention can be multi-layered. In this case, in addition to the layer made of the polypropylene homopolymer (A), other layers can be added as long as the object of the present invention is not impaired. Examples of materials for forming the other layers include olefin polymers other than the polypropylene homopolymer (A), gas barrier resins, and adhesive resins.

  Although the thickness of the polypropylene sheet of this invention is not specifically limited, Usually, 0.1-1.0 mm, Preferably it is 0.5-1.0 mm. When the thickness of the sheet is thicker than 1.0 mm, the transparency of the sheet may be inferior.

The polypropylene sheet according to the present invention has a HAZE per unit thickness (HAZE (t)) of 40% / mm or less, preferably 35% / mm or less, and the HAZE when the sheet is held at 40 ° C. for 8 days. The increase rate is 1.5 or less, preferably 1.2 or less.
HAZE (t) is obtained by the following equation.
HAZE (t) = (HAZE of sheet) / t [t = sheet thickness (mm)]
The HAZE increase rate is obtained by the following formula.
HAZE increase rate = (HAZE after holding at 40 ° C. for 8 days) / (HAZE immediately after molding)

(Molded body)
The molded body according to the present invention can be produced by molding the polypropylene sheet into a shape of a cup, a tray or the like by a conventionally known molding method such as vacuum molding, pressure forming, bulging molding, or plug assist molding. it can. As the molding conditions, conventionally known molding conditions can be employed.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, the measuring method of the physical property in an Example and a comparative example is as follows.

(M1) MFR (melt flow rate)
MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).
(M2) Melting point (Tm)
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). The endothermic peak in the third step measured here was defined as the melting point (Tm).

<Sample creation conditions>
Forming method: Press molding Mold: Thickness 0.2mm (sample is sandwiched between aluminum foil, press molding using mold)
Molding temperature: 240 ° C
Press pressure: 300 kg / cm ² , press time: 1 minute After press molding, the sheet is cooled with ice water, and about 0.4 g of the sheet is sealed in the following measurement container.
Measuring container: DSC PANS 10 μl BO-14-3015
DSC COVER BO14-3003

<Measurement condition>
1st step: Temperature is raised to 240 ° C. at 10 ° C./min and held for 10 minutes 2nd step: Temperature is lowered to 30 ° C. at 10 ° C./min 3rd step: Temperature is raised to 240 ° C. at 10 ° C./min

(M3) Mw / Mn measurement [weight average molecular weight (Mw), number average molecular weight (Mn)]
Measurement was performed as follows using GPC-150C Plus manufactured by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, and the column size is 7
. 5 mm, length 600 mm, column temperature 140 ° C., mobile phase o-dichlorobenzene (Wako Pure Chemical Industries) and BHT (Wako Pure Chemical Industries) 0.025 as an antioxidant The sample was moved at 1.0 ml / min using a mass%, the sample concentration was 0.1 mass%, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

(M4) Mesotriad fraction The mesotriad fraction (mm fraction) can be determined from a ¹³ C-NMR spectrum. Specifically, it measured by the method described in the international publication WO94 / 01609 pamphlet.

(M5) CFC
The cross chromatographic fractionation measurement of the propylene homopolymer (A) was carried out by cross chromatographic fractionation measurement (CFC) to measure the amount of components soluble in o-dichlorobenzene at 90 ° C.

Analysis of components soluble in orthodichlorobenzene at each temperature was performed by cross-chromatographic fractionation measurement (CFC). CFC was measured under the following conditions using the following apparatus equipped with a temperature rising elution fractionation (TREF) part for compositional fractionation and a GPC part for molecular weight fractionation, and the amount at each temperature was calculated.
Measuring device: CFC T-150A type, manufactured by Mitsubishi Yuka Co., Ltd.
Column: Shodex AT-806MS (× 3)
Dissolved solution: o-dichlorobenzene Flow rate: 1.0 ml / min
Sample concentration: 0.3 wt% / vol% (with 0.1% BHT)
Injection volume: 0.5 ml
Solubility: Complete dissolution Detector: Infrared absorption detection method, 3.42μ (2924 cm ^-1 ), NaCl plate Elution temperature: 0 to 135 ° C, 28 fractions
0, 10, 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 94, 97, 100, 103, 106, 109, 112, 115, 118, 121, 124, 127, 135 (℃)

For details of the measurement, the sample was heated at 145 ° C for 2 hours to dissolve, held at 135 ° C, then cooled to 0 ° C at 10 ° C / hr, and further held at 0 ° C for 60 minutes to coat the sample. It was. The temperature rising elution column volume is 0.83 ml, and the pipe volume is 0.07 ml. The detector used an infrared spectrometer MIRAN 1A CVF type (CaF ₂ cell) manufactured by FOXBORO, and infrared light of 3.42 μm (2924 cm ⁻¹ ) was detected by setting the absorbance mode with a response time of 10 seconds. The elution temperature was divided into 28 fractions from 0 ° C to 135 ° C. All temperature indications are integers. For example, the elution fraction at 94 ° C. indicates a component eluted at 91 to 94 ° C. 0 ℃
However, the molecular weight of the components that were not coated and the fraction eluted at each temperature were measured, and the molecular weight in terms of polypropylene was determined using a general calibration curve. The SEC temperature is 135 ° C., the internal standard injection volume is 0.5 ml, the injection position is 3.0 ml, and the data sampling time is 0.50 seconds. For data processing, the analysis program “CFC data processing (version 1.50
) ”.

(M6) 2,1-insertion ratio, 1,3-insertion ratio measurement
^{Using 13} C-NMR, according to the method described in JP-A-7-145212, the 2,1-insertion ratio of propylene and the 1,3-insertion ratio were measured.

(M7) Haze
Measured according to ASTM D-1003.
(M8) HAZE increase rate A sheet 10 cm × 10 cm is held in a thermostatic bath at 40 ° C. and RH 50% for 8 days. Then, after adjusting the condition in a room at 23 ° C. and a humidity of 50%, HAZE is measured to determine the HAZE increase rate.

[Production Example 1]
(1) Production of solid catalyst carrier SiO ₂ (Sunsphere H121 manufactured by AGC S-Itech) 300 in a 1 L branch flask
g was sampled 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 support)
In a glove box, 1.0 g of isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride was weighed into a 5 L four-necked flask. . The flask was taken out, 0.5 L of toluene and 2.0 L of MAO / SiO ₂ / toluene slurry prepared in (1) (100 g as a solid component) were added under nitrogen and stirred for 30 minutes to carry. The resulting isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99 in n-heptane. % Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 101 g of the solid catalyst component prepared in (2) above, 111 mL of triethylaluminum, and 80 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C. 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 An internal volume 58L jacketed circulation type tubular polymerizer is 30kg / hour of propylene, 5NL / hour of hydrogen, 6.2g / hour of the catalyst slurry produced in (3) as a solid catalyst component, triethylaluminum. 1.0 ml / hour was continuously supplied, and polymerization was performed 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 0.04 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  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 reactor, propylene was supplied at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.04 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  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 0.04 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  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 apparatus, propylene was supplied at 13 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.04 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (PP-1). The propylene polymer was obtained at 40 kg / h. The propylene polymer was vacuum dried at 80 ° C.

[Production Example 2]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization An internal capacity 58L jacketed circulation type tubular polymerizer is 30 kg / hour of propylene, 5 NL / hour of hydrogen, 4.0 g / hour of the catalyst slurry produced in (3) as a solid catalyst component, triethylaluminum. 1.0 ml / hour was continuously supplied, and polymerization was performed 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 vessel, propylene was supplied at 50 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.08 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.08 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  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 0.08 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  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 0.08 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (PP-2). The propylene polymer was obtained at 40 kg / h. The propylene polymer was vacuum dried at 80 ° C.

[Production Example 3]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a jacketed circulation tubular polymerizer with an internal capacity of 58 L, 30 kg / hour of propylene, 5 NL / hour of hydrogen, 3.5 g / hour of the catalyst slurry produced in (3) as a solid catalyst component, triethylaluminum 1.0 ml / hour was continuously supplied, and polymerization was performed 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 0.11 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  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 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  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 0.11 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 13 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (PP-3). The propylene polymer was obtained at 40 kg / h. The propylene polymer was vacuum dried at 80 ° C.

[Production Example 4]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a jacketed circulating tubular polymerizer with an internal capacity of 58 L, propylene is 30 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in (3) is 3.0 g / hour as a solid catalyst component, triethylaluminum. 1.0 ml / hour was continuously supplied, and polymerization was performed 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 vessel, propylene was supplied at 50 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.14 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.14 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  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 0.14 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  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 0.14 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (PP-4). The propylene polymer was obtained at 40 kg / h. The propylene polymer was vacuum dried at 80 ° C.

[Production Example 5]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a jacketed circulation 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) is 2.4 g / hour as a solid catalyst component, triethylaluminum 1.0 ml / hour was continuously supplied, and polymerization was performed 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 vessel, propylene was supplied at 50 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  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 0.21 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  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 reactor, propylene was supplied at 13 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.21 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (PP-5). The propylene polymer was obtained at 40 kg / h. The propylene polymer was vacuum dried at 80 ° C.

[Production Example 6]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In 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) is 1.9 g / hour as a solid catalyst component, triethylaluminum 1.0 ml / hour was continuously supplied, and polymerization was performed 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 0.31 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.31 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.

  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 0.31 mol%. Polymerization was performed at a polymerization temperature of 68 ° C. and a pressure of 2.9 MPa / G.

  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 0.31 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (PP-6). The propylene polymer was obtained at 40 kg / h. The propylene polymer was vacuum dried at 80 ° C.

Moreover, the following polymers manufactured using the Ziegler-Natta catalyst were used as polypropylene other than using the metallocene catalyst.
E110G: manufactured by Prime Polymer Co., Ltd. E111G: manufactured by Prime Polymer Co., Ltd. E-200GP: manufactured by Prime Polymer Co., Ltd. J-700GP: manufactured by Prime Polymer Co., Ltd. About PP-1 to PP-6 manufactured in the above production example and the above resin, The resin properties measured by the method described above are shown in the following table.

[Examples 1-5, Comparative Examples 1-5]
Sheets were molded using PP-1 to PP-6 produced in the above production examples and the above resin, and HAZE and HAZE increase rate were measured for the obtained sheets. The results are shown in the table below.

Claims (5)

A polypropylene homopolymer (A) obtained by using a metallocene catalyst and satisfying the following requirements (1) to (4) is melt-extruded at a resin temperature of 180 ° C. or more to form a molten sheet, and cooled at 50 to 100 ° C./second. It is a sheet having a film thickness of 0.1 to 1.0 mm obtained by cooling at a speed, and HAZE (HAZE (t)) per unit thickness is 40% / mm or less. A polypropylene sheet having an increase in HAZE of 1.5 or less when held at 8 ° C. for 8 days;
(1) Melt flow rate (MFR) is in the range of 0.1 to 10 g / 10 minutes (2) Melting point measured by differential scanning calorimeter (DSC) is 145 to 165 ° C. (3) Gel The molecular weight distribution index (Mw / Mn) measured by permeation chromatography (GPC) is 2 to 3.5. (4) The elution integrated amount up to 90 ° C. measured by the cross fractionation chromatography (CFC) 4% or less. The polypropylene sheet according to claim 1, wherein the metallocene catalyst is a catalyst containing a metallocene compound represented by the following general formula [III].

(In the formula, M is a Group 4 transition metal, R ¹ and R ³ are hydrogen atoms, R ² and R ⁴ are linear or branched alkyl groups having 1 to 5 carbon atoms, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group (provided that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms at the same time), and each may be the same The adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring;
Is a Group 14 element, R ¹³ and R ¹⁴ may be the same or different from each other, and are hydrocarbon groups of 1 to 20 carbon atoms that may be bonded to each other to form a ring, and Q is A halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand that can be coordinated by a lone electron pair is selected in the same or different combination, j is an integer of 1 to 4, and when j is 2 or more , Q may be the same as or different from each other. )   The molded object formed by thermoforming the polypropylene sheet of Claim 1 or 2.   The molded article according to claim 3, which is a tray.   The molded article according to claim 3, which is a cup.