JP5249797B2 - PTP packaging sheet - Google Patents

Description

  The present invention relates to a PTP packaging sheet, and more particularly to a PTP packaging sheet having a layer containing a propylene homopolymer that satisfies predetermined requirements.

  PTP packaging is a packaging form in which contents such as pharmaceuticals and foods are stored in a pocket created by thermoforming a plastic sheet, and aluminum foil coated with adhesive is heat-sealed so as to seal the opening. It is. The contents, such as medicines and foods, are taken out by pressing the pocket portion with a finger from the outside and pushing the foil with the contents.

The PTP packaging sheet used for PTP packaging is required to have the following characteristics.
(1) It must be transparent so that the state of the contents can be confirmed.
(2) To have a water vapor barrier property to ensure the quality of the contents.
(3) Thermoformability for forming according to the shape of the contents.
(4) Hygiene so that the contents are not contaminated by leakage from the sheet. Specifically, the n-heptane extraction amount of the sheet by the Ministry of Health and Welfare Notification No. 20 test is 150 ppm or less at 100 ° C.
(5) Low temperature impact resistance so that the pocket portion does not break due to impact applied to the sheet during storage.

  Conventionally, polyvinyl chloride resin has been used as a material for PTP packaging sheets, but due to environmental problems that harmful chlorine-containing substances are generated during incineration, their use has been difficult in recent years. .

For this reason, a polypropylene resin has begun to be used as a material to replace the polyvinyl chloride resin.
Conventionally, a polypropylene homopolymer is used for the polypropylene resin sheet for PTP packaging, and a petroleum resin is generally added to improve the water vapor barrier property. However, since petroleum resin is extracted by n-heptane extraction, there is a limit to the amount of addition for improving the water vapor barrier property.

  In order to improve the pocket formability (production rate) of the PTP packaging sheet, it is preferable to lower the thermoforming temperature. In order to lower the thermoforming temperature, it is conceivable to randomize the polypropylene used for the material. However, if random polypropylene is used, the water vapor barrier property of the resulting PTP packaging sheet is lowered. That is, in the PTP packaging sheet using the conventional polypropylene resin, there is a problem that it is difficult to balance thermoformability and water vapor barrier property.

  By the way, Patent Document 1 discloses an intermediate layer containing a crystalline polypropylene resin (a) and a petroleum resin (c), which are synthesized with a homogeneous catalyst and have a bending elastic modulus and a melting point in a specific range, and a specific ratio. In addition, a PTP laminated sheet comprising both outer layers containing a crystalline polypropylene resin (b) having a melting point in a specific range and petroleum resin (c) at a specific ratio is disclosed. In the laminated sheet for PTP described in Patent Document 1, thermoformability is improved by using a crystalline polypropylene resin (a) having a low melting point as a resin constituting the intermediate layer. No evaluation has been made on barrier properties and transparency. Patent Document 1 describes that the crystalline polypropylene resin (a) and the crystalline polypropylene resin (b) can be produced using a metallocene catalyst.

  In Patent Documents 2 and 3, the outer layer is composed of a mixture of polypropylene homopolymer and ethylene propylene copolymer, the sealing layer is composed of polypropylene homopolymer and ethylene propylene copolymer, and the intermediate layer is polypropylene homopolymer, ethylene propylene copolymer and petroleum resin or A PTP packaging sheet made of a thermoplastic elastomer is disclosed. In the techniques described in these documents, excellent transparency, thermoformability, rigidity, and impact resistance are achieved by optimizing the composition ratio of the polymer constituting each layer. No investigation has been made on the water vapor barrier property. Moreover, in the PTP packaging sheet described in these documents, the melting point and the melt flow rate (MFR), which are important parameters of the polymer used, are not defined at all.

JP 2002-19054 A JP-A-7-308998 JP 9-314770 A

  An object of this invention is to provide the sheet | seat for PTP packaging excellent in the balance of transparency, water vapor | steam barrier property, and thermoformability.

  If the propylene homopolymer produced using the metallocene catalyst system has the same melting point, the present inventors have less low crystallinity and low molecular weight components than the propylene polymer produced using the Ziegler-Natta catalyst system. In view of the high degree of crystallinity, the metallocene catalyst-based propylene homopolymer having a specific melting point was found to have an excellent balance between water vapor barrier properties and thermoformability.

That is, the following are mentioned as an aspect of the sheet | seat for PTP packaging of this invention for achieving the said objective.
Polymerized using a metallocene catalyst system with a melt flow rate of 0.1-10 g / 10 min, a melting point measured by DSC in the range of 155-167 ° C. A sheet for PTP packaging having a single layer structure, which comprises a propylene homopolymer (A) having a sum of 1,3-insertion bonds of 0.2 mol% or less and a petroleum resin.

  PTP packaging having a multilayer structure of at least three layers, wherein both outermost layers contain the propylene homopolymer (A), do not contain petroleum resin, and have a layer containing petroleum resin Sheet.

The multilayer PTP packaging sheet preferably has a three-layer structure.
The layer containing the petroleum resin preferably further contains the propylene homopolymer (A).

  Furthermore, as another preferred embodiment of the PTP packaging sheet of the present invention, the propylene homopolymer (A) is contained, and the layer (I) not containing petroleum resin is laminated on the layer (I). A PTP packaging sheet having a two-layer structure characterized by comprising a layer (II) containing a propylene homopolymer and a petroleum resin can be mentioned.

  The propylene homopolymer of the layer (II) is preferably the propylene homopolymer (A).

  Since the PTP packaging sheet of the present invention has a layer containing the propylene homopolymer (A), the balance between thermoformability and water vapor barrier properties is good without sacrificing transparency. Can be. In the PTP packaging sheet of the present invention, when the rigidity of the sheet is equal to that of the conventional product, the melting point of the propylene homopolymer (A) is lower than the melting point of the propylene polymer used in the conventional product. Therefore, the balance between thermoformability and water vapor barrier property can be improved.

The PTP packaging sheet of the present invention is polymerized using a metallocene catalyst system, has a melt flow rate of 0.1 to 10 g / 10 min, and has a melting point measured by DSC of 155 to 167.
A layer containing a propylene homopolymer (A) that is in the range of ° C. and the sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene is 0.2 mol% or less. Features. The PTP packaging sheet of the present invention may have a single layer structure or a multilayer structure.

[Propylene Homopolymer (A)]
The PTP packaging sheet according to the present invention has a melt flow rate of 0.1 to 10 g / 10 min, polymerized using a metallocene catalyst system, and a melting point measured by DSC of 155 to 1.
A layer having a propylene homopolymer (A) as an essential component within a range of 67 ° C., wherein the sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene is 0.2 mol% or less. Have. Hereinafter, each of these physical properties will be described.

<Melt flow rate>
The propylene homopolymer (A) used in the present invention has a melt flow rate (MFR) in the range of 1.0 to 10 g / 10 min, preferably 1 to 4 g / 10 min. MFR is ASTM
In accordance with D1238, measured at 230 ° C. and a load of 2.16 kg. The MFR can be adjusted by changing the polymerization temperature or using hydrogen as a chain transfer agent.
When the MFR of the propylene homopolymer (A) is within the above range, it is preferable because molding of the PTP sheet and pocket molding (secondary molding) can be carried out stably.

<Melting point>
The propylene homopolymer (A) used in the present invention has a melting point measured by DSC of 155 to 167 ° C, preferably 156 to 163 ° C, more preferably 156 to 160 ° 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 of propylene homopolymer (A) measured by DSC is less than 155 ° C., the rigidity of the PTP packaging sheet is insufficient, and when it exceeds 167 ° C., the polypropylene produced with a Ziegler-Natta catalyst It is not preferable because it becomes equivalent to.

<The sum of 2,1-insertion bond amount and 1,3-insertion bond amount of propylene>
The propylene homopolymer (A) used in the present invention is obtained from a ¹³ C-NMR spectrum, and the sum of propylene 2,1-insertion bond amount and 1,3-insertion bond amount is 0.2 mol% or less, Preferably it is 0.1 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 heterogeneous bond ratios 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 propylene homopolymer (A) is in the above range, the balance between thermoformability and rigidity is excellent.
Hereinafter, other physical properties of the propylene homopolymer (A) will be described.

<Mw / Mn>
The propylene homopolymer (A) used in the present invention has a molecular weight distribution index (Mw / Mn) measured by GPC of usually 3.5 or less, preferably 2.0 to 3.0. 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 or performing multistage polymerization using two or more polymerization tanks.

  When the Mw / Mn of the propylene homopolymer (A) is in the above range, since the low molecular weight component is small, there is little bleeding out, and the resulting PTP packaging sheet is excellent in transparency and blocking resistance.

<Integrated elution up to 90 ° C measured by CFC method>
The propylene homopolymer (A) used in the present invention has an integrated amount of elution up to 90 ° C. measured by a cross chromatographic fractionation measurement (CFC) method, usually 1% or less, preferably 0.5%, more preferably 0.3%. It is as follows. 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.

  When the integral amount of elution up to 90 ° C. measured by the CFC method of the propylene homopolymer (A) is in the above range, the propylene homopolymer (A) has few low molecular weight components, so there is little bleed out and the resulting PTP The packaging sheet is excellent in transparency, rigidity, and blocking resistance.

  By including the propylene homopolymer (A) having the physical properties described above in the layer constituting the PTP packaging sheet, a PTP packaging sheet excellent in transparency, water vapor barrier property and thermoformability is obtained. Can do.

  More specifically, the propylene homopolymer (A) used in the present invention has a water vapor barrier property as long as the melting point is the same as that of the propylene homopolymer produced with a Ziegler-Natta (ZN) catalyst. When the petroleum resin is contained in the layer constituting the PTP packaging sheet together with the propylene homopolymer, the amount of bleed of the petroleum resin is small. Furthermore, when the rigidity is set to be the same, the propylene homopolymer (A) has a lower melting point than the propylene homopolymer produced with the ZN-based catalyst, so the PTP packaging sheet of the present invention is thermoformed. The property is excellent. Further, the PTP packaging sheet of the present invention is superior in rigidity and water vapor barrier properties to the PTP packaging sheet disclosed in Patent Documents 1 to 3, which uses a propylene homopolymer produced using a metallocene catalyst. ing.

<Producing method of propylene homopolymer (A)>
Hereinafter, the manufacturing method of a propylene homopolymer (A) is demonstrated.
The method for producing the propylene homopolymer (A) used in the present invention is such that the propylene homopolymer (A) is polymerized using a metallocene catalyst system, the melt flow rate, the melting point measured by DSC, and 2 of propylene. , 1-insertion bond amount and 1,3-insertion bond amount, preferably as long as the other physical properties are satisfied, a ligand having a cyclopentadienyl skeleton is usually used. Produced by homopolymerizing propylene in the presence of a polymerization catalyst containing a metallocene compound in the molecule.

As a metallocene compound having a ligand having a cyclopentadienyl skeleton in the molecule,
From the chemical structure, two types, a non-bridged metallocene compound represented by the following general formula [I] and a bridged metallocene compound represented by the following general formula [II] 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、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く、
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, and when j is 2 or more, Qs may be the same as or different from each other;
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 - are shown (however, R ^a is a hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms And a nitrogen compound residue in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a hydrogenated hydrocarbon group, a hydrogen atom, a halogen atom or a nitrogen atom.

The polymerization catalyst preferably used in the present invention includes a bridged metallocene compound represented by the following general formula [III] disclosed in International Publication (WO01 / 27124) relating to the application of the present applicant, and an organometallic compound. And a metallocene catalyst comprising at least one compound selected from compounds capable of reacting with an organoaluminum oxy compound and a metallocene compound to form an ion pair, and, if necessary, 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 even 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 propylene 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 propylene 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 and cocatalyst, for example, at a polymerization temperature of 0 to 100 ° C. It can be produced by homopolymerizing propylene under polymerization conditions of normal pressure to 5 MPa gauge pressure.

[Single-layer PTP packaging sheet]
When the PTP packaging sheet of the present invention has a single layer structure, the PTP packaging sheet contains the propylene homopolymer (A) and a petroleum resin. When the PTP packaging sheet contains a petroleum resin, the water vapor barrier property and rigidity are improved.

  As the petroleum resin, known ones are used, and examples thereof include aromatic hydrocarbon resin, terpene resin, aliphatic saturated carbon resin, and hydrogenated cyclopentadiene aliphatic petroleum resin.

The content of the petroleum resin is usually 8% by mass or less, preferably 5 to 8% by mass with respect to the total amount of the propylene homopolymer (A) and the petroleum resin because of sanitary problems.
An elastomer (B) can be added to the single-layer PTP packaging sheet for the purpose of imparting characteristics such as impact resistance, heat sealability, transparency, and flexibility.

  The elastomer (B) includes ethylene / α-olefin random copolymer rubber (Ba), ethylene / α-olefin / non-conjugated polyene random copolymer (Bb), hydrogenated block copolymer (B−). c), propylene / α-olefin random copolymer rubber (Bd), other elastic polymers, and mixtures thereof.

The content of the elastomer (B) in the propylene resin composition containing the propylene homopolymer (A) and the elastomer (B) varies depending on the properties to be imparted, but is usually 1 to 10% by mass, preferably 1 to 5% by mass.

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

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. As said C3-C20 alpha-olefin, the same thing as the above is mentioned. Non-conjugated polyenes include 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-1,7-octadiene, 7- And chain-like non-conjugated dienes such as 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%. The MFR of the ethylene / α-olefin / non-conjugated polyene random copolymer (Bb) measured at 230 ° C. under a load of 2.16 kg is usually 0.05 g / 10 min or more, preferably 0.1-30 g / 10. Within minutes. 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.

上記式（ａ）または式（ｂ）におけるＸで示される重合ブロックを構成するモノビニル置換芳香族炭化水素の例としては、スチレン、α-メチルスチレン、p-メチルスチレン、
クロロスチレン、低級アルキル置換スチレン、ビニルナフタレン等のスチレンまたはその誘導体などが挙げられる。これらは一種単独で使用することもできるし、二種以上を組み合せて使用することもできる。

Examples of the monovinyl substituted aromatic hydrocarbon constituting the polymerization block represented by X in the above formula (a) or formula (b) include styrene, α-methylstyrene, p-methylstyrene,
Examples thereof include styrene such as chlorostyrene, lower alkyl-substituted styrene, vinyl naphthalene, and derivatives thereof. These can be used alone or in a combination of two or more.

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 alone or in a combination of two or more. 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 proportion 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, Kraton 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 Corporation), and the like.

The propylene / α-olefin random copolymer rubber (Bd) is a random copolymer rubber of propylene and an α-olefin having 4 to 20 carbon atoms. In the propylene / α-olefin random copolymer rubber (Bd), the molar ratio between the structural unit derived from propylene and the structural unit derived from α-olefin (structural unit derived from propylene / α-
The structural unit derived from olefin) is usually 95/5 to 5/95, preferably 80/20 to 20/80. Further, in the propylene / α-olefin random copolymer rubber (Bd), two or more α-olefins may be used, and when two or more α-olefins are used, one of them is Ethylene may be used. The MFR of propylene / α-olefin random copolymer rubber (Bd) measured at 230 ° C. under a load of 2.16 kg is usually 0.1 g / 10 min or more, preferably 0.5-30 g / 10 min. Is in range.

An elastomer (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
In the present invention, the elastomer (B) is usually used in an amount in the range of 0 to 10% by mass, preferably 0 to 5% by mass, with respect to 100% by mass of the propylene homopolymer (A).

  The PTP packaging sheet of the present invention is used together with the elastomer (B) or in place of the elastomer (B) for the purpose of imparting functions such as impact resistance, heat sealability, transparency, and high-speed extrusion sheet formability. Polyethylene resin (C) may be added.

For example, when imparting impact resistance while suppressing a decrease in transparency, a density of 0.900 to 0.930 kg / manufactured by copolymerizing ethylene and a C4 or higher α-olefin in the presence of a metallocene catalyst. It is preferred to add m ³ linear low density polyethylene.

As another example, when improving high speed extrusion moldability and thermoformability, high pressure polyethylene may be added. 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 (ASTMD
1238, 190 ° C., measured at a load of 2.16 kg) is usually in the range of 0.1 to 100 g / 10 min, preferably 0.1 to 20 g / 10 min. The density (ASTMD 1505) is usually in the range of 0.900 to 0.940 g / cm ³ , preferably 0.910 to 0.930 g / cm ³ .

  The content of the polyethylene resin (C) in the propylene-based resin composition containing the propylene homopolymer (A) and the polyethylene resin (C) varies depending on the properties to be imparted, but is usually 0 to 20% by mass, preferably It is 0-10 mass%, Most preferably, it exists in the range of 0-5 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 propylene homopolymer (A), an elastomer (B) and a polyethylene resin (C), the amount of the propylene homopolymer (A) varies depending on the properties to be imparted, Usually, it exists in the range of 80-99 mass% with respect to the whole propylene-type resin composition, Preferably it is in the range of 90-97 mass%. Moreover, the total amount of an elastomer (B) and a polyethylene resin (C) is 1-20 mass% normally with respect to 100 mass% of propylene homopolymers (A), Preferably it is 1-10 mass%. In addition, the ratio of elastomer (B) and polyethylene (C) can be arbitrarily adjusted according to the objective.

  The PTP packaging sheet of the present invention is a range that does not impair the purpose of the present invention, such as vitamins, antioxidants, heat stabilizers, weathering stabilizers, slip agents, antiblocking agents, mineral oils, etc. An additive may be included.

The thickness of the PTP packaging sheet of the present invention can be appropriately determined according to the purpose, and can be, for example, 50 to 500 μm.
Since the propylene homopolymer (A) is excellent in transparency and low temperature impact resistance, according to this PTP packaging sheet, it is possible to improve low temperature impact resistance without adding other elastomers, In addition, transparency, hygiene, and water vapor barrier properties can be improved. In addition, since the propylene homopolymer (A) has a low melting point and excellent formability at a low temperature, the PTP packaging sheet can improve the productivity during thermoforming while maintaining rigidity. In addition, water vapor barrier properties can be secured.

  The single-layer PTP packaging sheet of the present invention can be produced by a known method for producing a plastic sheet. For example, a resin material (propylene homopolymer (A), petroleum resin, elastomer (B), additive, etc.) is melt-kneaded using an extruder, pelletized, and then extruded from a molding machine capable of forming a sheet. It can be manufactured by forming a sheet-like melt and cooling it on a cast roll.

  In addition, the PTP packaging sheet of the present invention can be used for PTP packaging by forming a pocket portion using an existing PTP molding machine and then sealing aluminum foil or the like on the surface on which the concave surface is formed. it can.

[PTP packaging sheet having a multilayer structure]
The PTP packaging sheet of the present invention can be a multilayered sheet. There is no particular limitation on the number of layers.

The multilayer PTP packaging sheet of the present invention has a multilayer structure of at least three layers, both outermost layers containing a propylene homopolymer (A), no petroleum resin, water vapor barrier properties, etc. It is characterized by having a layer containing a petroleum resin for improving the viscosity. The content of the petroleum resin is usually 30% by mass or less, preferably 20% by mass or less, based on the total amount of the components constituting the petroleum resin-containing layer (hereinafter also simply referred to as layer (1)). . As a component other than the petroleum resin constituting the layer (1), a polymer such as polypropylene is exemplified.

  In particular, the multilayer PTP packaging sheet of the present invention preferably has a three-layer structure, and more preferably has a three-layer structure, and the layer (1) further contains a propylene homopolymer (A). . That is, since the layer (1) contains the propylene homopolymer (A), the balance of transparency, thermoformability, and rigidity is excellent.

  Thus, by making the sheet for PTP packaging into a multilayer structure and not containing petroleum resin in both outermost layers, the outer layer becomes a barrier layer for petroleum resin, and the content of petroleum resin is increased as compared with the case of a single layer structure ( Thereby, the water vapor barrier property of the PTP packaging sheet can be increased), and the hygiene is also improved.

Both the outermost layer and the layer (1) may contain an elastomer (B) and a polyethylene resin (C) as in the case of the single-layer PTP packaging sheet.
Moreover, as long as the objective of this invention is not impaired, both said outermost layers and layer (1) are vitamins, antioxidant, a heat stabilizer, a weather stabilizer, a slip agent, an antiblocking agent, as needed. Additives such as mineral oil may be included.

In the PTP packaging sheet having a multilayer structure of the present invention, the layers other than the two outermost layers and the layer (1) are made of conventional PT such as polypropylene homopolymer and ethylene propylene copolymer.
It can be formed of a material used for the P packaging sheet, or may be formed of a propylene homopolymer (A). By forming with the propylene homopolymer (A), a sheet for PTP packaging excellent in balance of transparency, thermoformability and rigidity can be obtained.

  In addition to these two outermost layers and the layer (1), the elastomer (B) and the polyethylene resin (C), vitamins, antioxidants, heat, and the like, as long as the object of the present invention is not impaired. Additives such as a stabilizer, a weathering stabilizer, a slip agent, an antiblocking agent, and mineral oil can be contained.

<Three-layer PTP packaging sheet>
Hereinafter, the structure of the PTP packaging sheet having a three-layer structure, which is a preferable embodiment of the PTP packaging sheet having a multilayer structure of the present invention, will be described. Examples of the three-layer structure include the following configurations.

  Both outer layers are layers containing a propylene homopolymer (A), and the intermediate layer is a layer composed of a propylene homopolymer (A) and a petroleum resin. By setting it as such a sheet structure, the sheet | seat for PTP packaging which further utilized the characteristic of said propylene homopolymer (A) can be obtained.

  Both outer layers are layers containing a propylene homopolymer (A), and the intermediate layer is a layer made of a polypropylene homopolymer polymerized with a Ziegler-Natta catalyst system and a petroleum resin. Even in such a sheet structure, since the water vapor barrier properties of both outer layers are excellent, a PTP packaging sheet having an excellent balance of transparency, water vapor barrier properties and thermoformability can be obtained.

  As described above, according to the PTP packaging sheet having a multilayer structure of the present invention, the effect of the single-layer structure PTP packaging sheet of the present invention is further improved, or in addition to the effect, a useful effect is further imparted. be able to.

  The thickness of the PTP packaging sheet having a three-layer structure of the present invention is usually 50 to 500 μm. As the ratio of the thickness of each layer, the thickness of each outer layer is preferably 5 to 30% and the thickness of the intermediate layer is preferably 40 to 90% with respect to the thickness of the entire sheet.

  The PTP packaging sheet having a multilayer structure of the present invention can be produced by a known method for producing a plastic sheet. For example, in the case of a PTP packaging sheet having a three-layer structure, resin materials (propylene homopolymer (A), petroleum resin, elastomer (B), additives, etc.) forming each layer are separately provided in three units. After melt-kneading using an extruder, the molten materials are merged in a T-die to form a melt having a three-layer structure by a co-extrusion method, and this is cooled on a cast roll. The thus manufactured three-layer PTP packaging sheet of the present invention is molded into a pocket portion using an existing PTP molding machine, and then aluminum foil or the like is sealed on the concave surface. By doing so, PTP packaging can be performed.

[Two-layer PTP packaging sheet]
The PTP packaging sheet of the present invention may have a two-layer structure.
The two-layer structure PTP packaging sheet of the present invention contains a propylene homopolymer (A), a layer (I) not containing a petroleum resin, and a propylene homopolymer laminated on the layer (I). And a layer (II) containing petroleum resin. The propylene homopolymer may be polymerized by a conventional Ziegler-Natta catalyst system, but is preferably a propylene homopolymer (A) from the viewpoint of a balance between thermoformability and rigidity.

And, by carrying out PTP packaging with the layer (I) as a layer in contact with the contents, the contamination of the contents due to the petroleum resin is prevented and the hygiene is improved, and a high water vapor barrier property is achieved. Can do. Further, since the structure is a two-layer structure, the manufacturing cost can be suppressed as compared with the case of a multilayer structure of three or more layers.

In the layer (I) and the layer (II), as in the case of the PTP packaging sheet having a single layer or a multilayer structure described above, an elastomer (B) and polyethylene may be used as necessary within the range not impairing the object of the present invention. Resin (C) and additives such as vitamins, antioxidants, heat stabilizers, weathering stabilizers, slip agents, antiblocking agents, mineral oils, and the like can be contained.

The thickness of the PTP packaging sheet having a two-layer structure of the present invention is usually 50 to 500 μm. As the ratio of the thickness of each layer, the thickness of the layer (I) is 95 to 5% relative to the thickness of the entire sheet, and the layer (II
) Is preferably 5 to 95%.

  The production method of the PTP packaging sheet having a two-layer structure is the same as the production method of the PTP packaging sheet having the three-layer structure described above, and the resin material (propylene homopolymer (A), petroleum resin, elastomer) forming each layer. (B), additives, etc.) are separately melt-kneaded using two extruders, and then the melted materials are joined in a T-die to form a melt having a two-layer structure by coextrusion. By forming and cooling on a cast roll, a PTP packaging sheet having a two-layer structure is obtained. The method of using the thus produced two-layer PTP packaging sheet of the present invention for PTP packaging is the same as described above.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example. The analysis method employed in the present invention is as follows.

Mw / Mn Measurement Mw / Mn (wherein Mw is a weight average molecular weight and Mn is a number average molecular weight) of a propylene homopolymer was measured as follows using GPC-150C Plus manufactured by Waters. The separation columns were TSKgel GMH6-HT and TSK gel GMH6-HTL, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase. Industrial) and 0.025 wt% BHT (Wako Pure Chemical Industries) as an antioxidant, moved at 1.0 ml / min, sample concentration 0.1 wt%, sample injection volume 500 microliters, differential refraction as detector A total was used. Standard polystyrene is converted to polypropylene using a general-purpose calibration method for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ using Tosoh Corporation, and for 1000 ≦ Mw ≦ 4 × 10 ⁶ using pressure chemical. did. The Mark-Houwink coefficients of polystyrene and polypropylene are the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)). Was used.

Melting point (Tm)
The melting point (Tm) of the propylene homopolymer was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak in the third step was defined as the melting point (Tm).

<Sample creation conditions>
Molding method: Press mold: Thickness 0.2mm (sample is sandwiched between aluminum foils, press mold 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 sheet is sealed in the following measurement container.
Measuring container: DSC PANS 10 μl BO-14-3015
DSC COVER BO14-3003.

(Measurement condition)
First step: Increase the temperature to 240 ° C at 10 ° C / min and hold for 10 min.
Second step: Decrease the temperature to 30 ° C at 10 ° C / min.
Third step: Increase the temperature to 240 ° C at 10 ° C / min.

[MFR (melt flow rate)]
The MFR of the propylene homopolymer was measured according to ASTM D1238 (230 ° C., load 2.16 kg).

Cross chromatographic fractionation measurement (CFC)
Measurement of the amount of the propylene homopolymer soluble in o-dichlorobenzene at 90 ° C. was performed by cross-chromatographic fractionation measurement (CFC).
Analysis of components soluble in orthodichlorobenzene at each temperature was performed by cross-chromatographic fractionation measurement (CFC). CFC is a composition of components that are soluble in orthodichlorobenzene at each temperature using the following equipment equipped with a temperature rising elution fractionation (TREF) part for compositional fractionation and a GPC part for molecular weight fractionation. The amount was calculated.
Measuring device: CFC T-150A, 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 (° C.).

Details of the measurement will be described below. The sample was heated at 145 ° C for 2 hours to dissolve and then 135
After maintaining at 0 ° C., the temperature was decreased to 0 ° C. at 10 ° C./hr, and further maintained at 0 ° C. for 60 minutes to coat the sample with the column. 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 with a wavelength 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. The molecular weight of components not coated even at 0 ° C. and the fraction eluted at each temperature were measured, and the molecular weight in terms of polypropylene was determined using a general calibration curve.
Data processing was performed using the analysis program “CFC data processing (version 1.50)” included with the device (data sampling time was 0.50 seconds).

Measurement of 2,1-insertion bond and 1,3-insertion bond
^{Using 13} C-NMR, the amount of 2,1-insertion bond and the amount of 1,3-insertion bond of propylene were measured according to the method described in JP-A-7-152212.

Young's modulus of the sheet
According to JIS K 6781, the Young's modulus of the sheets produced in the examples and comparative examples was measured. The tensile speed is 200 mm / min, and the distance between chucks is 80 mm.

Sheet Impact Test The sheets produced in the examples and comparative examples were sampled to 5 cm × 5 cm, and the surface impact strength was measured with an impact tester (a method in which a hammer is pushed up from the bottom) at a predetermined temperature (hammer conditions: Tip 1 inch).

Sheet haze (HAZE)
Measured according to ASTM D-1003.

Moisture permeability of sheet (water vapor barrier property)
The measurement was performed at 40 ° C. and 90% RH according to JIS Z0208.

It measured by the n-heptane elution test according to Ministry of Health and Welfare Notification No. 20 test.

Samples (30 cm × 30 cm sheet of) attached to thermoformability Asano Seisakusho vacuum-pressure forming machine, heating the sheet at a heater temperature 300 ° C., to measure the time until the moldable, manufactured existing polypropylene (Prime Polymer The difference from the moldable time of F-300SP) was defined as thermoformability.
Thermoformability (sec) = Thermoforming time (sec)-Thermoforming time of existing PP (sec)
The lower the value is, the shorter the value is, the lower the value, which means that the productivity of the PTP packaging sheet is excellent.

[Production Example 1]
(1) Production of solid catalyst carrier 300 g of SiO ₂ (Sunsphere H121 manufactured by AGC S-Tech) in a 1 L branch flask.
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 in 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 the mixture was 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 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 4.0 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 0.08 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 homopolymer (P-1). The resulting propylene homopolymer (P-1) was vacuum dried at 80 ° C. The properties of the resulting propylene homopolymer (P-1) are shown in Table 1.

[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.
<Main polymerization>
Propylene 30 kg / hour, hydrogen 5 NL / hour, 3.5 g / hour of catalyst slurry prepared in (3) as solid catalyst component, 1.0 ml / hour of triethylaluminum Was continuously fed and polymerized in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization 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 homopolymer (P-2). The resulting propylene homopolymer (P-2) was vacuum dried at 80 ° C. The properties of the resulting propylene homopolymer (P-2) are shown in Table 1.

[Production Example 3]
(1) Production of solid catalyst support 300 g of SiO ₂ (Sunsphere H121, manufactured by AGC S-Tech) was sampled in a 1-liter branch flask, and 800 ml of toluene was put into a slurry.

The slurry was then transferred to a 5 liter four-necked flask and 260 ml of toluene was added.
To this, 2830 ml of methylaluminoxane (hereinafter referred to as MAO) -toluene solution (10 wt% solution) was introduced and stirred at room temperature for 30 minutes. 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 component (support of metal catalyst component on support)
In a glove box, place a 3-liter 1-neck flask with a volume of 5 liters [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)] 2.0 g of zirconium dichloride was weighed. The flask was taken out of the glove box, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in the above (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry.

The obtained [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% substituted with n-heptane to give a final slurry volume of 4 .5 liters. This operation was performed at room temperature.

(3) Preparation of pre-polymerization catalyst 202 g of the solid catalyst component prepared in (2) above, 109 ml of triethylaluminum, and 100 liters of heptane were introduced into an autoclave equipped with a stirrer with an internal volume of 200 liters and kept at an internal temperature of 15 to 20 ° C. Then, 2020 g of ethylene was introduced and reacted 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 was 2 g / liter. This prepolymerized catalyst contained 10 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization In a jacketed circulation type 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 3.5 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 0.10 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 0.10 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 0.10 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 0.10 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 homopolymer (P-3). The resulting propylene homopolymer (P-3) was vacuum dried at 80 ° C. The properties of the resulting propylene homopolymer (P-3) are shown in Table 1. Table 1 also shows the characteristics of commercially available polypropylene (F-300SP manufactured by Prime Polymer) manufactured with a Ziegler catalyst.

［実施例１］
製造例１で製造されたプロピレン単独重合体（Ｐ−１）９３質量部と石油樹脂（OPPERA
ＰＲ１０３Ｊ（エクソンモービル有限会社商標））７質量部とを合わせて１００質量部に対して、熱安定剤IRGANOX1010（チバガイギー（株）商標）０．１質量部、熱安定剤IRGAFOS168（チバガイギー（株）商標）０．１質量部、ステアリン酸カルシウム０．１質量
部をタンブラーにて混合後、ナカタニ機械（株）製二軸押出機（同方向2軸混練機）を用
いて２３０℃にて溶融混練してペレット状のポリプロピレン樹脂組成物（ＰＰ−１）を調製し、ＧＭエンジニアリング（株）製Ｔダイシート成形機（ダイ幅２００ｍｍ，リップギャップ１ｍｍ）にて、押出温度２４０℃，チルロール温度５０℃（タッチロール成形），
加工速度７m/minの条件で厚み３００μｍの単層シートを製造した。得られたシートのＨ
ＡＺＥ、ヤング率、インパクト強度、透湿度、ｎ−ヘプタン可溶分を測定した。結果を表２に示す。

[Example 1]
93 parts by mass of propylene homopolymer (P-1) produced in Production Example 1 and petroleum resin (OPPERA
PR103J (ExxonMobil Co., Ltd.)) 7 parts by mass and 100 parts by mass of thermal stabilizer IRGANOX1010 (Ciba Geigy Co., Ltd.) 0.1 part by mass, thermal stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) ) After 0.1 parts by mass and 0.1 parts by mass of calcium stearate were mixed with a tumbler, they were melt kneaded at 230 ° C. using a twin screw extruder (same direction twin screw kneader) manufactured by Nakatani Machinery Co., Ltd. A pellet-shaped polypropylene resin composition (PP-1) was prepared, and the extrusion temperature was 240 ° C. and the chill roll temperature was 50 ° C. (touch roll) using a T-die sheet molding machine (die width 200 mm, lip gap 1 mm) manufactured by GM Engineering Co., Ltd. Molding),
A single-layer sheet having a thickness of 300 μm was produced under a processing speed of 7 m / min. H of the obtained sheet
AZE, Young's modulus, impact strength, moisture permeability, and n-heptane soluble content were measured. The results are shown in Table 2.

[Example 2]
The same procedure as in Example 1 was conducted except that 93 parts by mass of the propylene homopolymer (P-1) was changed to 93 parts by mass of the propylene homopolymer (P-2) produced in Production Example 2. The results are shown in Table 2.

[Example 3]
The same procedure as in Example 1 was conducted except that 93 parts by mass of the propylene homopolymer (P-1) was changed to 93 parts by mass of the propylene homopolymer (P-3) produced in Production Example 3. The results are shown in Table 2.

[Comparative Example 1]
Except that 93 parts by mass of the propylene homopolymer (P-1) in Example 1 was changed to a commercially available PP resin (F-300SP manufactured by Prime Polymer Co., Ltd .: MFR = 3 g / 10 min, Tm = 161 ° C.). The same was done. The results are shown in Table 2.

［実施例４］
製造例３で製造されたプロピレン単独重合体（Ｐ−３）８０質量部と石油樹脂（OPPERA
ＰＲ１０３Ｊ（エクソンモービル有限会社商標））２０質量部とを合わせて１００質量部に対して、熱安定剤IRGANOX1010（チバガイギー（株）商標）０．１質量部、熱安定剤IRGAFOS168（チバガイギー（株）商標）０．１質量部、ステアリン酸カルシウム０．１質
量部をタンブラーにて混合後、ナカタニ機械（株）製二軸押出機（同方向2軸混練機）を
用いて２３０℃にて溶融混練してペレット状のポリプロピレン樹脂組成物（ＰＰ−３）を調製し、ＧＭエンジニアリング（株）製２種３層Ｔダイシート成形機（ダイ幅２００ｍｍ，リップギャップ１ｍｍ）にて、押出温度２４０℃，チルロール温度５０℃（タッチロー
ル成形），加工速度７m/minの条件で、中間層にＰＰ−３、両外層にＰ−３を使用し、各
層の厚みの比率が１０／８０／１０％であり、厚み３００μｍの３層シートを製造した。得られたシートのＨＡＺＥ、ヤング率、インパクト強度、透湿度、ｎ−ヘプタン可溶分を測定した。結果を表３に示す。

[Example 4]
80 parts by mass of the propylene homopolymer (P-3) produced in Production Example 3 and petroleum resin (OPPERA
PR103J (ExxonMobil Co., Ltd.)) 20 parts by mass and 100 parts by mass of thermal stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.) 0.1 part by mass, thermal stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) ) After 0.1 parts by mass and 0.1 parts by mass of calcium stearate were mixed with a tumbler, they were melt kneaded at 230 ° C. using a twin screw extruder (same direction twin screw kneader) manufactured by Nakatani Machinery Co., Ltd. A pellet-shaped polypropylene resin composition (PP-3) was prepared, and the extrusion temperature was 240 ° C. and the chill roll temperature was 50 with a GM Engineering Co., Ltd. 2-type 3-layer T-die sheet molding machine (die width 200 mm, lip gap 1 mm). PP-3 is used for the intermediate layer and P-3 is used for both outer layers under conditions of ℃ (touch roll molding) and processing speed of 7 m / min, and the ratio of the thickness of each layer is 10/80/10% It was prepared three-layer sheet having a thickness of 300 [mu] m. The obtained sheet was measured for HAZE, Young's modulus, impact strength, moisture permeability, and n-heptane soluble content. The results are shown in Table 3.

[Comparative Example 2]
In Example 4, 80 parts by mass of the propylene homopolymer (P-3) was changed to 80 parts by mass of a commercially available PP resin (F-300SP manufactured by Prime Polymer Co., Ltd .: melting point 161 ° C., MFR = 3 g / 10 min). The same procedure was performed except that the resin composition (PP-4) was used for the intermediate layer and F-300SP was used for both outer layers. The results are shown in Table 3.

  Since the PTP packaging sheet of the present invention is excellent in the balance of transparency, water vapor barrier property, thermoformability, and rigidity, it can be suitably used as a medical and food PTP packaging.

Claims (6)

Polymerized using a metallocene catalyst system with a melt flow rate of 0.1-10 g / 10 min, a melting point measured by DSC in the range of 155-167 ° C. A propylene homopolymer (A) having a sum of 1,3-insertion bond amount of 0.2 mol% or less,
A sheet for PTP packaging having a single-layer structure, comprising a petroleum resin. A multilayer structure of at least three layers,
Both outermost layers contain the propylene homopolymer (A) according to claim 1 and do not contain a petroleum resin,
A PTP packaging sheet comprising a layer containing a petroleum resin.   The PTP packaging sheet according to claim 2, which has a three-layer structure.   The PTP packaging sheet according to claim 2, wherein the layer containing the petroleum resin further contains the propylene homopolymer (A) according to claim 1. A layer containing the propylene homopolymer (A) according to claim 1 and containing no petroleum resin (I
)When,
A PTP packaging sheet having a two-layer structure comprising a layer (II) containing a propylene homopolymer and a petroleum resin laminated on the layer (I).   The sheet for PTP packaging according to claim 5, wherein the propylene homopolymer of the layer (II) is the propylene homopolymer (A) according to claim 1.