JP2018203297A - Sterilization container - Google Patents

Abstract

To provide a container having heat resistance durable to high temperature sterilization at 120°C or higher, and also preferable transparency, blocking resistance and shock resistance.SOLUTION: A container includes the layer of a resin composition including 70-95 mass% of a propylene resin (A) meeting following requirements (a1)-(a2), and 5-30 mass% of an ethylenic resin (B) meeting all of following requirements (b1)-(b3) (where, the total amount of (A) and (B) is 100 mass%). (a1) MFR at 230°C, 2.16 kg load: 0.3-5.0 g/10 min., (a2) Ethylene content: 3.0-10.0 mass%, (b1) MFR at 190°C, 2.16 kg load: 0.3-3.0 g/10 min., (b2) Density: 890-915 kg/m, (b3) Molecular weight distribution (Mw/Mn) obtained by GPC measuring: 3.0 or less.SELECTED DRAWING: None

Description

  The present invention relates to a sterilization container having both heat resistance capable of withstanding high-temperature sterilization at 120 ° C. or higher and good transparency, blocking resistance, and impact resistance.

Some containers for food and medicine are subjected to heat sterilization with the contents in the container.
Currently used food packaging containers for heat sterilization are commonly called retort pouches, and include surface protection / printing layers (PET film, etc.), barrier layers (Al foil, etc.), heat seal layers (polypropylene, polyethylene, etc.) Polyolefin film) is bonded to each other through an adhesive, and the heat seal layer is inside the pouch, so that it comes into contact with the contents. For this reason, the heat seal layer has heat seal strength necessary to protect the contents during heat sterilization and storage, sufficient impact resistance that can withstand dropping of the pouch filled with the contents, and heat resistance that can withstand heat sterilization. Sex is required.

  In addition, in recent years, needs such as heating with a microwave oven and visual recognition of contents are increasing, and in many cases, Al foil is not used as a barrier layer. In that case, the transparency of the polyolefin film used for the heat seal layer is high. May be emphasized.

  In addition, currently used medical containers for heat sterilization include hard containers made of glass, polyethylene, and polypropylene, and soft bags made of polyvinyl chloride or polyethylene containing a plasticizer. The above-mentioned rigid container needs to introduce air using a vent needle or an infusion set with a vent when dripping the content liquid such as blood and chemicals, and the contents are contaminated by these instruments. May occur. On the other hand, unlike a hard container, the soft bag does not require the introduction of air when dripping the content liquid, and the bag itself is squeezed by the atmospheric pressure as the content liquid is dripped. There are advantages, such as the property and the small volume of waste. However, polyvinyl chloride has problems such as the plasticizer contained and the toxicity of residual monomers.

As a material used for heat seal layer film for heat sterilization with emphasis on transparency,
・ Polyethylene: LLDPE and HDPE with relatively high density
Polypropylene: Random PP blended with an elastomer component for impact improvement is used.

In patent document 1, it is a container which has a layer which consists of a linear polyethylene obtained by copolymerizing ethylene and a C3-C12 alpha olefin, and this linear polyethylene has (i) density. in the range of 0.918~0.940g / cm ^3, (ii) a molecular weight distribution measured by GPC (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) of 1.5 to 3.0 The layer composed of the linear polyethylene is within the range, (a) haze after retort sterilization is 30% or less, (b) deformation start temperature (Td [° C.]) is higher than sterilization temperature. It is characterized by high temperature. However, since this container uses only a polyethylene-based resin, there is a problem that it cannot withstand high-temperature sterilization at 120 ° C. or higher.

Patent Document 2 discloses a polypropylene film for retort that is excellent in impact resistance and blocking resistance at low temperatures. This polypropylene film for retort is a film in which propylene / ethylene block copolymer is 96 to 99 wt% and high density polyethylene is 1 to 4 wt%, and the propylene / ethylene block copolymer is the following (a ) To (c).
(A) Melting | fusing point is 157-164 degreeC.
(B) The xylene soluble content is 16 to 25%.
(C) MFR is 1.0 to 3.0 g / 10 min.

Patent Document 3 discloses a polypropylene resin composition suitable as a material for a retort food packaging film. The polypropylene resin composition of Patent Document 3 comprises a polymer part of a monomer whose main component is propylene having an intrinsic viscosity of 2.0 (dL / g) or more, and a copolymer part of propylene and ethylene. A composition (provided that (A) and 94 to 98 parts by weight of a propylene-based copolymer (A) and 2 to 6 parts by weight of an ethylene polymer (B) having a density of 0.920 g / cm ³ or more) (B) is obtained by melt-kneading in the presence of the organic peroxide (C), and the melt flow rate is 1.5 (g / 10 min) or more. Features.

The polypropylene film of Patent Document 4 contains (a) 80 to 96% by weight of a propylene / ethylene block copolymer, (b) an α-olefin having 3 to 10 carbon atoms and ethylene, and a density of 0.86 to 2 to 10% by weight of an ethylene / α-olefin copolymer elastomer of 0.90 g / cm ³ and (c) 2 to 10% by weight of a polyethylene-based polymer having a density of 0.94 to 0.97 g / cm ^3. A polypropylene-based film obtained by melt-forming a resin composition, wherein (a) the propylene / ethylene block copolymer has a proportion of a 20 ° C. xylene insoluble part of 75 to 90% by weight, and an intrinsic viscosity ([ η] _H ) is 1.8 to 2.2 dl / g, the intrinsic viscosity ([η] _EP ) of the soluble part is 2.5 to 3.3 dl / g, and [η] _H + 0.6 ≦ _{[η] EP} der It is characterized in. The skin resistance and bending whitening resistance after retorting the sample at 135 ° C. for 30 minutes are evaluated.

  Patent Document 5 discloses a decane insoluble content, a decane soluble content, an intrinsic viscosity of the decane insoluble content and a decane soluble content, 60 to 80% by weight of the propylene-based polymer (A) having an MFR in a specific range, and a single site. Nucleation for 20 to 40% by weight of ethylene / α-olefin copolymer (B) polymerized using a catalyst and having a specific density and a specific MFR, and a total of 100 parts by weight of (A) and (B) A propylene-based resin composition containing 0.1 to 0.4 parts by weight of an agent is disclosed. This propylene-based resin composition has rigidity, low-temperature impact resistance, and transparency even when it is thinner and lighter than conventional products when manufacturing molded articles such as food packaging containers. It is said to be excellent.

JP-A-8-244791 Japanese Patent Laid-Open No. 10-158463 JP 2009-13332 A JP 2012-172124 A Japanese Patent No. 5511865

  In fact, the above-described conventional materials cannot provide a container that satisfies all of transparency, heat resistance, rigidity, and blocking resistance. In particular, there is a great demand for providing a container having resistance to heat sterilization at a temperature of 120 ° C. or more and having transparency, rigidity, and blocking resistance.

  An object of the present invention is to provide a container having both heat resistance capable of withstanding high-temperature sterilization at 120 ° C. or higher and good transparency, blocking resistance and impact resistance.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that one of the containers used by heat sterilizing a composition containing a specific propylene resin and a specific ethylene resin at a specific mixing ratio. By using it as a layer, it discovered that the container excellent in transparency, heat resistance, rigidity, and blocking resistance was obtained, and completed this invention.
That is, the present invention includes the following modes [1] to [6].

[1] 70 to 95% by mass of a propylene-based resin (A) that satisfies the following requirements (a1) to (a2);
(A1) MFR under load of 230 ° C. and 2.16 kg is 0.3 to 5.0 g / 10 minutes (a2) Ethylene content is 3.0 to 10.0% by mass
5-30% by mass of an ethylene-based resin (B) satisfying all the following requirements (b1) to (b3);
(B1) MFR under 190 ° C. and 2.16 kg load is 0.3 to 3.0 g / 10 minutes (b2) Density is 890 to 915 kg / m ³
(B3) The molecular weight distribution (Mw / Mn) determined by GPC is 3.0 or less.
(However, the sum of (A) and (B) is 100% by mass).

[2] The container according to [1], wherein the propylene-based resin (A) further satisfies the following requirement (a3).
(A3) The melting point measured by DSC is 135 ° C. or higher and 170 ° C. or lower.

[3] The propylene-based resin (A) is
[Α1] which is a propylene homopolymer component and / or propylene / ethylene copolymer component having a propylene content of 100 to 94% by mass and an ethylene content of 0 to 6% by mass, and 100 to 75% by mass,
1 to 25% by mass of [α2], which is a propylene / ethylene copolymer component having a propylene content of 85 to 70% by mass and an ethylene content of 15 to 30% by mass, [1] Or the container as described in [2].

[4] The propylene resin (A) further includes the following requirements (a4) to (a6):
(A4) A pentad fraction determined by NMR measurement of a component insoluble in room temperature n-decane (Dinsol) is 95 mol% or more, and (a5) of a component soluble in room temperature n-decane (Dsol), 135 The intrinsic viscosity ([η] sol) in decalin at 2.5 ° C. is 2.5 dl / g to 4.0 dl / g,
(A6) The content (C2sol) of the structural unit derived from ethylene in the component (Dsol) soluble in room temperature n-decane is 20 to 30% by mass,
The container according to any one of [1] to [3], wherein

  [5] The container according to any one of [1] to [4], which can be heat-sterilized at 120 ° C. or higher.

[6] A method for producing the propylene-based resin (A) according to [3] above,
Including at least one stage polymerization process;
The first stage includes a step of (co) polymerizing 100 to 94% by mass of propylene and 0 to 6% by mass of ethylene (provided that the total of propylene and ethylene is 100% by mass),
Furthermore, in the second stage, a step of copolymerizing 85 to 70% by mass of propylene and 15 to 30% by mass of ethylene (provided that the total of propylene and ethylene is 100% by mass),
The first stage (co) polymer component and the second stage copolymer component have a mass ratio of 75 to 100/25 to 0 in the first stage / second stage, and a propylene resin (A The process for producing a propylene-based resin (A) is characterized by including a copolymerization step of propylene and ethylene in which the ethylene content is 3.0 to 10.0% by mass.

  According to the present invention, there is provided a container having both heat resistance that can withstand high temperature sterilization at 120 ° C. or higher and good transparency, blocking resistance, and impact resistance.

The container according to the present invention is a food packaging container typified by a retort pouch or a medical container such as an infusion bag or an infusion bottle, and relates to a container that contains contents that require high-temperature sterilization at 120 ° C. or higher.
As for the container concerning this invention, the at least 1 layer consists of a specific propylene-type resin composition. Hereinafter, the propylene-based resin composition will be described in detail.

[Propylene-based resin composition]
The propylene resin composition according to the present invention includes 70 to 95% by mass of the propylene resin (A) satisfying the following requirements (a1) to (a2), and 5 to 30% by mass of the following (b1) to (b3). ) Containing an ethylene-based resin (B) that satisfies all the requirements of (A) and (B) as a sum of 100% by mass.
(A1) MFR under load of 230 ° C. and 2.16 kg is 0.3 to 5.0 g / 10 minutes (a2) Ethylene content is 3.0 to 10.0% by mass
(B1) MFR under 190 ° C. and 2.16 kg load is 0.3 to 3.0 g / 10 minutes (b2) Density is 890 to 915 kg / m ³
(B3) The molecular weight distribution (Mw / Mn) determined by GPC is 3.0 or less.

<Propylene resin (A)>
The MFR of the propylene-based resin (A) at 230 ° C. and a load of 2.16 kg is within a range of 0.3 to 5.0 g / 10 minutes. If the MFR is less than 0.3 g / 10 min, the extrusion moldability of the composition obtained by mixing with the ethylene-based resin (B) may deteriorate, and if it exceeds 5.0 g / 10 min, Drawdown increases. The MFR of the propylene-based resin (A) is preferably 0.5 g / 10 minutes or more. Moreover, it is preferable that MFR is 4.0 g / 10min or less.

  The propylene-based resin (A) contains a propylene / ethylene copolymer component and has an ethylene content in the range of 3.0 to 10.0% by mass. As the propylene-based resin (A), [α1], which is a propylene homopolymer component and / or propylene / ethylene copolymer component having a propylene content of 100 to 94% by mass and an ethylene content of 0 to 6% by mass, is 100 to 75. It is preferable to contain 0% to 25% by mass of [α2], which is a propylene / ethylene copolymer component having a propylene content of 85 to 70% by mass and an ethylene content of 15 to 30% by mass. This preferred propylene-based resin shows a block copolymer of component [α1] and component [α2], or a block copolymer of a propylene homopolymer component and a propylene / ethylene copolymer component in component [α1], Hereinafter, it is called propylene-based resin (A1). The “content” referred to here corresponds to the amount of raw material charged, as shown in the production method described later.

The propylene resin (A) preferably further satisfies the following requirement (a3).
(A3) The melting point measured by DSC is 135 ° C. or higher and 170 ° C. or lower.
When the melting point is lower than 135 ° C, the heat resistance of the resulting container is lowered, and the transparency after sterilization at 120 ° C or higher may be deteriorated.

The propylene resin (A) preferably further satisfies the following requirements (a4) to (a6).
(A4) A pentad fraction determined by NMR measurement of a component insoluble in room temperature n-decane (Dinsol) is 95 mol% or more, and (a5) of a component soluble in room temperature n-decane (Dsol), 135 The intrinsic viscosity ([η] sol) in decalin at 2.5 ° C. is 2.5 dl / g to 4.0 dl / g,
(A6) The content (C2sol) of the structural unit derived from ethylene in the component (Dsol) soluble in room temperature n-decane is 20 to 30% by mass.

  Each measurement of requirements (a4) to (a6) is performed by separating a component (Dinsol) that is insoluble in room temperature n-decane and a soluble component (Dsol) from the propylene-based resin (A). . As a separation method, 200 ml of n-decane is added to 5 g of a sample of the propylene-based resin (A), dissolved by heating at 145 ° C. for 30 minutes, then cooled to 20 ° C. over about 3 hours and left for another 30 minutes. The precipitate (Dinsol) is filtered off. The filtrate is put in about 3 times amount of acetone, and the component (Dsol) dissolved in n-decane is precipitated and separated by filtration.

  The requirement (a4) is a mmmm pentad fraction according to NMR (nuclear magnetic resonance spectroscopy) of Dinsol, and shows stereoregularity in Dinsol. Dinsol is mainly a propylene homopolymer component and has crystallinity. Good blocking resistance is obtained when the pentad fraction determined by NMR measurement of this Dinsol is 95 mol% or more.

On the other hand, Dsol is mainly a propylene / ethylene copolymer component and does not exhibit crystallinity or has low crystallinity. When Dsol has an intrinsic viscosity ([η] sol) in decalin of 135 ° C. of 2.5 dl / g to 4.0 dl / g, good blocking resistance and fish eye level can be obtained. [η] sol is preferably 2.8 dl / g to 3.6 dl / g.
Moreover, favorable transparency and the heat seal strength after a retort are obtained because content (C2sol) of the structural unit derived from ethylene in Dsol is 20-30 mass%. C2sol is preferably 20 to 28% by mass.

<Method for producing propylene-based resin (A)>
Although the manufacturing method of the propylene-type resin (A) used by this invention is not specifically limited as long as said requirements (a1)-(a2) are satisfy | filled, The polymerization process of the copolymerization component of propylene and ethylene is included. . In particular, the following method is preferable as a method for producing the propylene-based resin (A1).

Including at least one stage polymerization process;
The first stage includes a step of (co) polymerizing 100 to 94% by mass of propylene and 0 to 6% by mass of ethylene (provided that the total of propylene and ethylene is 100% by mass),
Furthermore, in the second stage, a step of copolymerizing 85 to 70% by mass of propylene and 15 to 30% by mass of ethylene (provided that the total of propylene and ethylene is 100% by mass),
The first stage (co) polymer component and the second stage copolymer component have a mass ratio of 75 to 100/25 to 0 in the first stage / second stage, and a propylene resin (A ) Includes a copolymerization step of propylene and ethylene in which the ethylene content is 3.0 to 10.0% by mass.

  In particular, it is preferable to homopolymerize propylene in the first stage and to copolymerize propylene and ethylene in the second stage.

  In addition, the polymerization is preferably carried out using a hydrogen gas serving as a chain transfer agent in the presence of a catalyst. As the catalyst, a catalyst containing a metallocene compound or a Ziegler-Natta catalyst can be used. By using a Ziegler-Natta catalyst, a propylene-based resin (A) containing a propylene homopolymer component having excellent stereoregularity can be obtained. As the Ziegler-Natta catalyst used for the polymerization, various known catalysts can be used.

  For example, a catalyst comprising (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donating pair, (b) an organometallic compound catalyst component, and (c) an organosilicon compound catalyst component is used. it can.

<Ethylene resin (B)>
(B1): MFR of the ethylene-based resin (B) under 190 ° C. and 2.16 kg load is within a range of 0.3 to 3.0 g / 10 minutes. If the MFR is less than 0.3 g / 10 minutes, the extrusion moldability of the composition obtained by mixing with the propylene-based resin (A) may deteriorate, and if it exceeds 3.0 g / 10 minutes, Drawdown increases. The MFR of the ethylene resin (B) is preferably 0.5 g / 10 min or more. Moreover, it is preferable that MFR is 2.5 g / 10min or less.

(B2): The density of the ethylene-based resin (B) is in the range of 890 to 915 kg / m ³ . When the density of the ethylene resin (B) is low, the blocking resistance is deteriorated, and when it is high, the impact resistance may be deteriorated.
(B3): Further, the molecular weight distribution (Mw / Mn) determined by GPC of the ethylene-based resin (B) is 3.0 or less.

  The ethylene resin (B) is not particularly limited as long as it satisfies the requirements (b1) to (b3) at the same time, and a commercially available ethylene polymer can be used. In particular, an ethylene / α-olefin copolymer obtained by copolymerizing ethylene with an α-olefin having 4 or more carbon atoms is preferable, and a copolymer of ethylene and 1-hexene is more preferable. The ethylene resin (B) may satisfy the requirements (b1) to (b3) at the same time by combining two or more kinds of ethylene / α-olefin copolymers.

<Method for producing propylene-based resin composition>
The propylene-based resin composition according to the present invention is a propylene-based polymer (A) of 70 to 95 mass%, preferably 75 to 100 mass% in total of 100 mass% of the propylene-based resin (A) and the ethylene-based resin (B). 90 mass% and 5-30 mass% of the said ethylene-type resin (B), Preferably it contains in the range of 10-25 mass%.
A composition in which the amount of the propylene-based resin (A) is less than 70% by mass deteriorates blocking resistance and rigidity. On the other hand, if it exceeds 95% by mass, the amount of the ethylene-based resin (B) becomes too small and the transparency and impact resistance deteriorate.

  The propylene-based resin composition according to the present invention further includes an antioxidant, a nucleating agent, a lubricant, a flame retardant, an anti-blocking agent, a colorant, an inorganic or organic substance that is usually added to the olefin polymer as required. Various additives such as fillers and various synthetic resins may be added as long as the object of the present invention is not impaired.

  The propylene resin composition according to the present invention can be prepared by various known production methods. For example, the propylene polymer (A) and the ethylene resin (B) obtained in advance are blended with various additives as necessary in the amounts described above, for example, Henschel mixer, ribbon blender, Banbury mixer A method of mixing using various known devices such as, or after mixing, 170 to 300 ° C., preferably using various known kneaders such as a single screw extruder or twin screw extruder, Brabender or roll, etc. And a method of melt-kneading at 190 to 250 ° C.

[container]
The container concerning this invention has at least 1 layer which consists of said propylene-type resin composition. In particular, food packaging containers represented by retort pouches or medical containers such as infusion bags and infusion bottles are suitable as containers that are subjected to heat sterilization treatment at 120 ° C. or higher.

  These containers can be produced by first producing a sheet or film having at least one layer composed of the propylene-based resin composition, and further shaping the obtained sheet or film into a desired shape.

  Such a sheet or film can be produced by using a propylene-based resin composition and various known molding methods, for example, a film molding machine equipped with a T-die or a circular die at the tip of an extruder.

  The thickness of the sheet or film can be variously determined depending on the application, but is preferably in the range of 10 μm to 2 mm, and more preferably in the range of 10 to 800 μm. The propylene-based resin composition according to the present invention is excellent in impact resistance at low temperatures even as a relatively thin film.

  Such a sheet or film may be an unstretched film or a stretched film, but an unstretched film is preferred.

  Such a sheet or film can be used as a container material such as a retort pouch even in a single layer, but by laminating with stretched or unstretched polyamide film, uniaxial or biaxially stretched polyester film, aluminum foil or paper, etc., a multilayer film Or it can be used as a sheet.

  A bottle-shaped container can be manufactured by blow molding.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this Example.
First, the used propylene resin (A) and ethylene resin (B) will be described.

<Propylene resin (A)>
[Production Example 1] (Propylene-based resin (A): Production of [PP1])
(1) Preparation of solid titanium catalyst component An anhydrous magnesium chloride 95.2 g, decane 442 ml and 2-ethylhexyl alcohol 390.6 g were heated at 130 ° C. for 2 hours to make a homogeneous solution, and then this solution was mixed with anhydrous phthalic anhydride. 21.3 g of acid was added and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added and stirred at the same temperature for 2 hours. Retained.
After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2.3 mass% titanium, 61 mass% chlorine, 19 mass% magnesium, and 12.5 mass% DIBP.

(2) Preparation of prepolymerization catalyst 87.5 g of the solid titanium catalyst component prepared in (1), 19.5 mL of triethylaluminum, and 10 L of heptane were charged into an autoclave with a stirrer having an internal volume of 20 L, and an internal temperature of 15 to 20 ° C. The mixture was charged with 263 g of propylene and allowed to react with stirring for 100 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane to obtain a solid catalyst component concentration of 0.7 g / L to obtain a catalyst slurry.

(3) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene 30 kg / hour, hydrogen 40 NL / hour, 0.44 g / hour of the prepolymerization catalyst slurry produced in the above (2) as a solid titanium catalyst component, Triethylaluminum (4.9 mL / hour) and dicyclopentyldimethoxysilane (1.6 mL / hour) were continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 70 ° C., and the pressure was 3.3 MPa / G (G = gauge pressure).
The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 70 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 1.5 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.
The obtained slurry was transferred to a transfer pipe having an internal volume of 2.4 L, gasified and gas-solid separated, and then the polypropylene homopolymer powder was sent to a gas phase polymerizer having an internal volume of 480 L. / Propylene block copolymerization was performed. Propylene, ethylene, and hydrogen are continuously added so that the gas composition in the gas phase polymerization reactor is ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene = 0.078 (molar ratio). Supplied. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.0 MPa / G.
The obtained powder was gas-solid separated and vacuum dried at 80 ° C. As a result, a propylene-based resin (A) [PP1] having a polypropylene part and an ethylene / propylene copolymer part was obtained.

[Production Example 2] (Production of propylene-based resin (A) [PP2])
(1) Preparation of Magnesium Compound The reaction vessel with a stirrer having an internal volume of 500 L was sufficiently replaced with nitrogen gas, and after charging 97.2 kg of ethanol, 640 g of iodine and 6.4 kg of metal magnesium, the mixture was stirred under reflux conditions. The reaction was carried out until no hydrogen gas was generated from the system to obtain a body-like reaction product. The target magnesium compound (solid product) was obtained by drying the reaction solution containing the solid reaction product under reduced pressure.

(2) Preparation of solid titanium catalyst component In a reaction tank equipped with a stirrer with an internal volume of 500 L sufficiently substituted with nitrogen gas, 30 kg of the magnesium compound obtained in (1) above (not pulverized), 150 L of purified heptane, 4.5 L of silicon tetrachloride and 4.3 L of diethyl phthalate were charged. The system was kept at 90 ° C., 144 L of titanium tetrachloride was added with stirring and reacted at 110 ° C. for 2 hours, and then the solid components were separated and washed with purified heptane at 80 ° C. Further, 228 L of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours, and then sufficiently washed with purified heptane to obtain a solid titanium catalyst component.

(3) Preparation of prepolymerization catalyst 230 L of purified heptane was charged into a reaction tank with an internal volume of 500 L, and further 25 kg of the solid catalyst component obtained in the above (2) was added. After adding 0.6 mol of triethylaluminum and 0.4 mol of cyclohexylmethyldimethoxysilane to 1 mol of atom, propylene is added at a partial pressure of propylene of 29.4 kPa / G (0.3 kg / cm ² G). The mixture was introduced until the reaction temperature reached 25 ° C. for 4 hours. After completion of the reaction, the solid catalyst component was washed several times with purified heptane, supplied with carbon dioxide and stirred for 24 hours to obtain a prepolymerized catalyst slurry.

(4) Polymerization In a polymerization apparatus (R-1) with a stirrer having an internal volume of 200 L, the prepolymerization catalyst slurry of the above (3) was converted into Ti atom at 3 mmol / hr and triethylaluminum at 413 mmol / hr (7.5 The cyclohexylmethyldimethoxysilane was supplied at 105 mmol / hr (1.9 mmol / kg-PP) at a mmol / kg-PP), and propylene was polymerized at a polymerization temperature of 80 ° C. and a total pressure of 3 MPa · G. At this time, propylene was adjusted to 99.93 mol% and hydrogen was adjusted to a gas composition of 0.07 mol% and supplied. Subsequently, powder was continuously extracted from R-1 and transferred to a polymerization apparatus (R-2) with an internal volume of 200 L equipped with a stirrer. In R-2, propylene and ethylene were copolymerized at a polymerization temperature of 50 ° C. and a total pressure of 1.1 MPa · G. At this time, propylene was adjusted to 81.4 mol%, ethylene was adjusted to 14.5 mol%, and hydrogen was adjusted so as to have a gas composition of 4.1 mol%. In this way, a propylene resin (A) [PP2] was obtained.

[Production Example 3] (Production of propylene-based resin (A) [PP3])
(1) Preparation of the solid titanium catalyst component and (2) preparation of the prepolymerized catalyst were carried out in the same manner as in [Production Example 1].
(3) Main polymerization 300 L of liquefied propylene was charged into a polymerization tank equipped with a stirrer with an internal volume of 500 L, and while maintaining this liquid level, 130 kg / h of liquefied propylene and 0.9 g / l of prepolymerized catalyst slurry as a solid titanium catalyst component were used. h, 4.9 ml / h of triethylaluminum and 8.3 ml / h of dicyclopentyldimethoxysilane were continuously fed, and polymerization was performed at a temperature of 70 ° C. Further, hydrogen and ethylene were continuously supplied so that the hydrogen concentration in the gas phase portion in the polymerization tank was 0.4 mol% and the ethylene concentration was 2.0 mol%. The obtained slurry was deactivated, and then sent to a liquid propylene washing tank, and the polypropylene powder was washed. Thereafter, propylene was evaporated to obtain a powdery propylene / ethylene copolymer (PP3).

[Production Example 4] (Production of propylene-based resin (A) [PP4])
(1) Preparation of the solid titanium catalyst component and (2) preparation of the prepolymerized catalyst were carried out in the same manner as in [Production Example 1].
(3) Main polymerization 300 L of liquefied propylene was charged into a polymerization tank equipped with a stirrer with an internal volume of 500 L, and while maintaining this liquid level, 130 g / h of liquefied propylene and 0.7 g of prepolymerized catalyst slurry as a solid titanium catalyst component were used. / H, triethylaluminum was continuously supplied at 4.0 ml / h, and dicyclopentyldimethoxysilane was continuously supplied at 6.8 ml / h, and polymerization was performed at a temperature of 70 ° C. Further, hydrogen and ethylene were continuously supplied so that the hydrogen concentration in the gas phase portion in the polymerization tank was 1.0 mol% and the ethylene concentration was 2.2 mol%. The obtained slurry was deactivated, and then sent to a liquid propylene washing tank, and the polypropylene powder was washed. Thereafter, propylene was evaporated to obtain a powdery propylene / ethylene copolymer (PP4).

[Production Example 5] (Production of propylene-based resin (A) [PP5])
(1) Preparation of Magnesium Compound The inside of a reactor equipped with a stirrer (internal volume 500 L) was sufficiently replaced with nitrogen gas, and 97.2 kg of ethanol, 640 g of iodine, and 6.4 kg of magnesium metal were added and refluxed with stirring. The reaction was continued until no hydrogen gas was generated from the system to obtain a solid reaction product. The reaction solution containing the solid reaction product was dried under reduced pressure to obtain the target magnesium compound (solid catalyst carrier).

(2) Preparation of solid catalyst component In a reactor equipped with a stirrer sufficiently substituted with nitrogen gas (internal volume 500 L), 30 kg of the magnesium compound (not pulverized), 150 L of purified heptane (n-heptane), silicon tetrachloride 4.5 L and 5.4 L of di-n-butyl phthalate were added. The system was maintained at 90 ° C., and 144 L of titanium tetrachloride was added while stirring and reacted at 110 ° C. for 2 hours. Then, the solid component was separated and washed with purified heptane at 80 ° C. Further, 228 L of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours, and then sufficiently washed with purified heptane to obtain a solid catalyst component.

(3) Preparation of pre-polymerization catalyst 230 L of purified heptane was charged into a reaction tank with an internal volume of 500 L, and the solid titanium catalyst component was 25 kg, and triethylaluminum was added to the titanium atom in the solid titanium catalyst component. 0.0 mol / mol and dicyclopentyldimethoxysilane were supplied at a rate of 1.8 mol / mol. Thereafter, propylene was introduced until the partial pressure of propylene reached 29.4 kPa / G (0.3 kg / cm ² G ) and reacted at 25 ° C. for 4 hours. After completion of the reaction, the solid titanium catalyst component was washed several times with purified heptane, further supplied with carbon dioxide and stirred for 24 hours to obtain a prepolymerized catalyst slurry.

(4) Polymerization In a polymerization apparatus with a stirrer having an internal volume of 200 L, the prepolymerization catalyst slurry was converted to 3 mmol / hr in terms of titanium atoms in the components, triethylaluminum at 4 mmol / kg-PP, and dicyclopentyldimethoxysilane at 1 mmol / kg-. Propylene and ethylene were reacted at a polymerization temperature of 80 ° C. and a polymerization pressure (total pressure) of 2.75 MPa / G (28 kg / cm ² G), respectively. At this time, the ethylene concentration in the polymerization apparatus was adjusted to 2.4 mol% and the hydrogen concentration was set to 5.5 mol% so that the desired ethylene content and molecular weight were obtained.

Table 1 shows the physical properties of the propylene resins [PP1] to [PP5] obtained in Production Examples 1 to 5.
The measurement method for each evaluation item is as follows:
Melt flow rate (MFR: g / 10 minutes)
Based on JIS K7210, the measurement was performed under the conditions of 230 ° C. and 2.16 kg load (kgf).

・ D _sol and D _insol fractionation method (decane soluble fractionation method)
200 ml of n-decane was added to 5 g of a sample of the final product (that is, the propylene-based resin (A) of the present invention) and dissolved by heating at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble portion: D _insol ) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane (precipitate (A)). The precipitate (A) and acetone were separated by filtration, and the precipitate (D _sol ) was dried. Even when the filtrate side was concentrated to dryness, no residue was observed.

・ Ethylene content (mass%: wt%)
For the propylene polymer (A), the skeleton concentration derived from ethylene in D _sol (C2sol) in the first stage polymer (in the case of propylene-ethylene copolymer), second stage (final product) In order to measure, 20-30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, and then carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed. Propylene, ethylene and α-olefin were quantitatively determined from the dyad chain distribution. For example, propylene - if ethylene _{copolymer, PP = S αα, EP =} S αγ + S αβ, using _{EE = 1/2 (S βδ} + S δδ) + 1 / 4S γδ, the following equation (the eq- Obtained by 1) and (Eq-2).
Propylene (mol%) = (PP + 1 / 2EP) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)]… (Eq-1)
Ethylene (mol%) = (1 / 2EP + EE) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)]… (Eq-2)
In addition, the unit of ethylene content in a present Example was converted and expressed in the mass%.

-Melting | fusing point Crystal melting | fusing point can be calculated | required by measuring on the following measuring conditions using a differential scanning calorimeter (DSC, the Perkin-Elmer company make (Diamond DSC)) according to JIS-K7121. The peak of the endothermic peak in the third step when the measurement was performed under the following measurement conditions was defined as the crystalline melting point (Tm). When there are a plurality of endothermic peaks, the peak of the endothermic peak where the peak height is maximum is defined as the crystalline melting point (Tm).
(Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample amount: 5mg
Sample shape: Press film (molded at 230 ° C, thickness 400 µm)
Sample pan: Aluminum sample pan with a flat bottom First step: The temperature is increased from 30 ° C. to 200 ° C. at 10 ° C./min and held for 10 min.
Second step: The temperature is lowered to 30 ° C. at 10 ° C./min.
Third step: The temperature is raised to 200 ° C. at 10 ° C./min.

・ Dinsol pentad fraction (mmmm: [%])
It is one of the indexes of the stereoregularity of the polymer, and the pentad fraction (mmmm,%) whose microtacticity was examined was ¹³ C assigned based on Macromolecules 8,687 (1975) in the above Dinsol component. -It calculated from the peak intensity ratio of the NMR spectrum. The 13C-NMR spectrum was measured using an EX-400 device manufactured by JEOL, based on TMS, at a temperature of 130 ° C., and an o-dichlorobenzene solvent.

・ Intrinsic viscosity [η] sol
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of granulated pellets are dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0)

<Ethylene resin (B)>
The following PE1 to PE6 were used as the ethylene resin (B).
PE1: Evolue (registered trademark) SP0510, manufactured by Prime Polymer Co., Ltd. PE2: manufactured in accordance with the following Production Example 6. PE3: Evolue (registered trademark) SP2120, manufactured by Prime Polymer Co., Ltd. PE4: Ultozex (registered trademark) 1540L, (stock) ) Prime polymer PE5: Tafmer (registered trademark) A-0585X, Mitsui Elastomers Singapore manufactured PE6: Tafmer (registered trademark) P-0480, Mitsui Elastomers Singapore manufactured

[Production Example 6] (Production of PE2)
-Preparation of Olefin Polymerization Catalyst (2) 40 L of dehydrated hexane was charged into a 110 LSUS vessel equipped with a stirrer with sufficient nitrogen substitution, and brine (refrigerant) was passed through the jacket. Next, 2.04 L of methylalumoxane / hexane solution (3 mol in terms of Al atom) and then 4.8 g (6 mmol in terms of Zr atom) represented by the following chemical formula (1) were inserted and stirred for 5 The reaction was carried out at around 0 ° C. for 2 hours or longer to obtain an olefin polymerization catalyst (2).

-Production of ethylene / 1-hexene copolymer Dehydrated and purified n-hexane was fed at a flow rate of 19.9 L / hour into one feed port of a 130 L stirring blade-added-pressure continuous polymerization reactor that had been sufficiently purged with nitrogen. Continuously supplied, and at the same time to another supply port of the continuous polymerization reactor, hydrogen was continuously supplied at a flow rate of 4.0 NL / h, ethylene at a flow rate of 5.3 kg / hour, and hexene-1 at a flow rate of 7.7 kg / hour. Supplied. Then, the olefin polymerization catalyst (2) obtained above was continuously supplied at a flow rate of 0.025 mmol / hour, under the conditions of a polymerization temperature of 165 ° C., a total pressure of 2.9 MPa / G, and a stirring rotational speed of 256 rpm. Continuous solution polymerization was performed. The refrigerant was circulated through a jacket provided on the outer periphery of the polymerization reactor, the gas phase portion was forcibly circulated using a separately installed gas blower, and the polymerization reaction heat was removed by cooling it with a heat exchanger. .

  The hexane solution containing the ethylene / hexene-1 copolymer produced by polymerization under the above conditions is provided with a discharge port provided at the bottom of the polymerization reactor so as to maintain an average solution volume of 30 L in the polymerization reactor. The ethylene / hexene-1 copolymer was continuously discharged at a rate of 5.0 kg / hour.

Table 2 shows the physical properties of the ethylene-based resins [PE1] to [PE6] to be used. The measurement method for each evaluation item is as follows:
Melt flow rate (MFR: g / 10 minutes)
Based on JIS K7210, the measurement was performed under the conditions of 190 ° C. and 2.16 kg load (kgf).
・ Density [kg / m ³ ]
Based on JIS K7112, the strand obtained at the time of MFR measurement was heat-treated at 100 ° C. for 1 hour, and further allowed to stand at room temperature for 1 hour, and then measured by a density gradient tube method.
Mw / Mn measurement [weight average molecular weight (Mw), number average molecular weight (Mn)]
It measured as follows using GPC-150C Plus by Waters. The separation columns were TSKgel GMH6-HT and TSKgel 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, Ltd.) was used as the mobile phase. Kogyo Co., Ltd.) and 0.025% by mass of BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1% by mass, and the sample injection amount Was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene used was made 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 .

○ Examples and Comparative Examples <Film>
For 100 parts by mass of the resin in which the propylene-based resin (A) and the ethylene-based resin (B) shown above are blended in the ratios shown in Tables 3 to 5, an antioxidant (Irganox (registered trademark) 1010, BASF Corporation) 750 ppm, heat stabilizer (Irgaphos (registered trademark) 168, manufactured by BASF) 750 ppm, calcium stearate 500 ppm, and kneaded with a twin-screw kneader (Kobe Steel, screw diameter 30 mm) to obtain a resin composition It was. Furthermore, using a single layer casting machine having a screw diameter of 75 mmφ, a film having a film thickness of 70 μm was formed at a cast roll temperature of 40 ° C. and a take-up speed of 55 m / min (30 m / min for Table 5). The obtained film was aged at 40 ° C. for 24 hours and then evaluated for physical properties. A result is combined with Tables 3-5, and is shown. The method of each evaluation is as follows.

-Haze It measured based on ASTM D-1003 (JIS K7105).
-Impact resistance of film (-20 ° C film impact)
The film is sampled to 5cm x 5cm, and the impact strength is measured at -20 ° C with an impact tester (a method in which a hammer with a tip of 1 inch (2.5cm) is pushed from the bottom to the top with a load of 3.0J). Evaluated.

-Blocking strength The chill roll surfaces of the film of 10 cm in MD direction × 10 cm in TD direction are overlapped and held in a thermostatic bath at 50 ° C. under a load of 200 g / cm ² for 3 days. Then, after conditioning in a room at 23 ° C. and 50% humidity for 24 hours or more, the peel strength when peeled at a tensile speed of 200 mm / min was measured, and the value obtained by dividing the peel strength by the test piece width was the blocking coefficient. And blocking resistance was evaluated. Here, the smaller the blocking coefficient, the better the blocking resistance.

-MD direction tensile elastic modulus Measured with the following test piece and measurement conditions using a tensile tester. Test piece: JIS K6781
80mm between chucks, tensile speed 200mm / min, measurement temperature 23 ° C

-Appearance after sterilization treatment at 121 ° C The obtained film was sterilized at 121 ° C and then visually evaluated. Sterilization was performed under the following conditions.
(Sterilization conditions: equipment, atmosphere, time, etc.)
The evaluation criteria are as follows.
○: No problem with whitening and shrinkage after sterilization.
Δ: Partial whitening or shrinkage observed after sterilization ×: Fully whitening or shrinkage observed after sterilization

<Bottle>
With respect to 100 parts by mass of the resin in which the propylene resin (A) and the ethylene resin (B) shown above were blended in the ratios shown in Tables 6 to 8, an antioxidant (Irganox (registered trademark) 1010, BASF Corporation) 750 ppm, heat stabilizer (Irgaphos (registered trademark) 168, manufactured by BASF) 750 ppm, calcium stearate 500 ppm, and kneaded with a twin-screw kneader (Kobe Steel, screw diameter 30 mm) to obtain a resin composition It was. Further, hollow molding was performed under the following molding conditions to form a single-layer / cylindrical hollow container having an internal volume of 600 ml, a bottle weight of 30 g, and a body thickness of 400 μm.
-Molding machine: manufactured by Nippon Steel Co., Ltd., model number: JEB-7 hollow molding machine-Cylinder temperature of the extruder: 200 ° C
-Die temperature: 200 ° C
・ Mold temperature: 15 ℃
・ Resin extrusion rate: 7kg / h

The method of each evaluation is as follows.
-Haze It measured based on ASTM D-1003 (JIS K7105). The measurement was carried out on the barrel part of the bottle.

-Charpy impact strength The Charpy impact strength was measured according to JIS K7111, under the following conditions, and measured using a 4 mm-thick injection test piece.
Temperature: 0 ° C
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
The notch is machined.

-Blocking property After putting the obtained bottle into the tray made from SUS and sterilizing at 121 degreeC, blocking property was observed.
○: No fusion between the bottle and the SUS tray is recognized. ×: Fusion between the bottle and the SUS tray is recognized.

MD direction tensile elastic modulus / appearance after sterilization at 121 ° C. Evaluation was performed in the same manner as the film.

Claims (6)

70 to 95% by mass of a propylene-based resin (A) that satisfies the following requirements (a1) to (a2)
(A1) MFR under load of 230 ° C. and 2.16 kg is 0.3 to 5.0 g / 10 minutes (a2) Ethylene content is 3.0 to 10.0% by mass
5-30% by mass of an ethylene-based resin (B) satisfying all the following requirements (b1) to (b3);
(B1) MFR under 190 ° C. and 2.16 kg load is 0.3 to 3.0 g / 10 minutes (b2) Density is 890 to 915 kg / m ³
(B3) The molecular weight distribution (Mw / Mn) determined by GPC is 3.0 or less.
(However, the sum of (A) and (B) is 100% by mass). The container according to claim 1, wherein the propylene-based resin (A) further satisfies the following requirement (a3).
(A3) The melting point measured by DSC is 135 ° C. or higher and 170 ° C. or lower. The propylene resin (A) is
[Α1] which is a propylene homopolymer component and / or propylene / ethylene copolymer component having a propylene content of 100 to 94% by mass and an ethylene content of 0 to 6% by mass, and 100 to 75% by mass,
The propylene content is 85 to 70% by mass and the ethylene content is 15 to 30% by mass, and [α2] which is a propylene / ethylene copolymer component having 0 to 25% by mass is included. Or the container of 2. The propylene-based resin (A) further has the following requirements (a4) to (a6):
(A4) A pentad fraction determined by NMR measurement of a component insoluble in room temperature n-decane (Dinsol) is 95 mol% or more, and (a5) of a component soluble in room temperature n-decane (Dsol), 135 The intrinsic viscosity ([η] sol) in decalin at 2.5 ° C. is 2.5 dl / g to 4.0 dl / g,
(A6) The content (C2sol) of the structural unit derived from ethylene in the component (Dsol) soluble in room temperature n-decane is 20 to 30% by mass,
The container of any one of Claims 1-3 which satisfy | fills.   The container according to any one of claims 1 to 4, which can be heat-sterilized at 120 ° C or higher. It is a manufacturing method of the propylene-type resin (A) of Claim 3, Comprising:
Including at least one stage polymerization process;
The first stage includes a step of (co) polymerizing 100 to 94% by mass of propylene and 0 to 6% by mass of ethylene (provided that the total of propylene and ethylene is 100% by mass),
Furthermore, in the second stage, a step of copolymerizing 85 to 70% by mass of propylene and 15 to 30% by mass of ethylene (provided that the total of propylene and ethylene is 100% by mass),
The first stage (co) polymer component and the second stage copolymer component have a mass ratio of 75 to 100/25 to 0 in the first stage / second stage, and a propylene resin (A A process for producing a propylene-based resin (A), comprising a step of copolymerizing propylene and ethylene so that the ethylene content is 3.0 to 10.0%.