JP7073161B2 - container - Google Patents

Description

The present invention relates to a container, and more specifically, to a sterilized container having heat resistance capable of withstanding high temperature sterilization at 121 ° C. or higher, and good transparency, blocking resistance, and impact resistance.

A container for accommodating a chemical solution is used for injecting a chemical solution or the like, and in recent years, a container made of flexible plastic has become the mainstream as the container. This type of container has the advantages of being easy to handle and easy to dispose of.
As the container, a container made of polyolefin such as polyethylene or polypropylene, which has established safety because it comes into direct contact with a chemical solution or the like, is widely used.

As such a container, for example, Patent Document 1 describes a polyethylene-based container, and Patent Documents 2 and 3 describe a polypropylene-based container.

Japanese Unexamined Patent Publication No. 2017-186499 Japanese Unexamined Patent Publication No. 2014-208772 Special Table 2016-50078 Gazette

The fact is that the conventional container does not satisfy all of transparency, heat resistance, impact resistance and blocking resistance. In particular, there is a great demand for the provision of a hygienic and easy-to-check container that does not cause deformation, blocking, large wrinkles, etc. even if it is sterilized by heating at a temperature of 121 ° C or higher, and that does not impair transparency. There is.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a container having heat resistance, good transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher.

As a result of diligent studies to solve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved according to the following configuration example, and has completed the present invention.
The configuration example of the present invention is as follows.

[1] Propylene-based resin (A) 57 to 75% by mass satisfying the following requirements (a1) to (a4),
Ethylene resin (B) 10 to 25% by mass satisfying the following requirements (b1) to (b3),
50 mol% or more of the propylene-derived structural unit and the α-olefin-derived structural unit having 2, 4 to 20 carbon atoms (however, the total of the propylene-derived structural unit and the α-olefin-derived structural unit is 100 mol%. ), And 10 to 18% by mass of the propylene-based elastomer resin (C) satisfying the following requirements (c1) to (c4).
(However, the total of (A) to (C) is 100% by mass), a container containing a layer made of a resin composition.
(A1) MFR at 230 ° C. under a load of 2.16 kg for 0.3 to 5.0 g / 10 minutes (a2) Ethylene content is 3.0 to 8.0% by mass.
(A3) The melting point measured by DSC is 135 to 150 ° C.
(A4) Rockwell hardness (JIS K7202) is 65 to 90.
(B1) MFR at 190 ° C. under a load of 2.16 kg for 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 3.5 or less. (C1) Shore A hardness (ASTM D2240) is 65 to 90.
(C2) Melting point is 130-170 ° C.
(C3) Density (ASTM D1505) is 860-875 kg / m ³
(C4) The glass transition temperature measured by DSC is -25 to -35 ° C.

[2] After high-temperature sterilization at 121 ° C for 15 minutes, the transmittance of light with a wavelength of 450 nm by the ultraviolet-visible absorbance measurement method based on the 17th revised Japanese Pharmacopoeia transparency test method 1 is 70% or more. The container according to [1].

[3] The container according to [1] or [2], wherein the average thickness of the body of the container is 0.01 to 1.0 mm.
[4] The container according to any one of [1] to [3], wherein the body of the container is a single layer.

[5] The container according to any one of [1] to [4], which is for medical use or food use.
[6] The container according to any one of [1] to [5] for infusion.

According to the present invention, sterilization under high temperature conditions of 121 ° C or higher does not cause blocking, wrinkles or deformation, heat resistance that can withstand high temperature sterilization of 121 ° C or higher, good transparency, impact resistance and It is possible to provide a container having both blocking resistance.

FIG. 1 is a schematic schematic diagram of an infusion bottle according to an embodiment of the container according to the present invention. (A1) is a front view of the infusion bottle, (a2) is a sectional view taken along the line AA of the bottle body. FIG. 2 is a schematic schematic diagram of an infusion bag according to an embodiment of the container according to the present invention. (B1) is a front view of the infusion bag, and (b2) is a sectional view taken along the line BB of the bag body.

≪Container≫
The container according to the present invention (hereinafter, also referred to as “the present container”) includes a layer made of the resin composition.
Since this container contains such a layer, it is a container that exerts the above-mentioned effect.

<Resin composition>
The resin composition is
Propylene resin (A) 57 to 75% by mass that satisfies all of the following requirements (a1) to (a4),
Ethylene resin (B) 10 to 25% by mass that satisfies all of the following requirements (b1) to (b3),
50 mol% or more of the propylene-derived structural unit and the α-olefin-derived structural unit having 2, 4 to 20 carbon atoms (however, the total of the propylene-derived structural unit and the α-olefin-derived structural unit is 100 mol%. ), And 10 to 18% by mass of the propylene-based elastomer resin (C) satisfying all of the following requirements (c1) to (c4).
(However, the total of (A) to (C) is 100% by mass).
The composition can be suitably used as a material for various containers.
(A1) MFR at 230 ° C. under a load of 2.16 kg for 0.3 to 5.0 g / 10 minutes (a2) Ethylene content is 3.0 to 8.0% by mass.
(A3) The melting point measured by DSC is 135 to 150 ° C.
(A4) Rockwell hardness (JIS K7202) is 65 to 90.
(B1) MFR at 190 ° C. under a load of 2.16 kg for 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 3.5 or less. (C1) Shore A hardness (ASTM D2240) is 65 to 90.
(C2) Melting point is 130-170 ° C.
(C3) Density (ASTM D1505) is 860-875 kg / m ³
(C4) The glass transition temperature measured by DSC is -25 to -35 ° C.

<Propene resin (A)>
The propylene-based resin (A) is not particularly limited as long as it satisfies all of the above requirements (a1) to (a4).
The resin composition may contain two or more kinds of propylene-based resins (A).

The melt flow rate (MFR) of the propylene resin (A) at 230 ° C. under a load of 2.16 kg is 0.3 to 5.0 g / 10 minutes, preferably 0.5 g / 10 minutes or more, and is preferable. Is 3.0 g / 10 minutes or less.
When the MFR is in the above range, a resin composition having excellent moldability can be easily obtained.
If the MFR is less than 0.3 g / 10 minutes, the extrudability of the resin composition is poor, and if it exceeds 5.0 g / 10 minutes, drawdown is likely to occur during blow molding.
The MFR can be measured by a method based on JIS K7210.

The propylene-based resin (A) contains at least a structural unit derived from ethylene, and its content (ethylene content) is 3.0 to 8.0% by mass, preferably 4.0 to 7.0% by mass. More preferably, it is 4.0 to 6.0% by mass.
By using the propylene resin (A) having an ethylene content in the above range, it has an excellent balance of heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher, and is particularly transparent and transparent. A container having excellent flexibility can be easily obtained.
The "ethylene content" referred to here may be calculated from the amount of ethylene charged, or may be a value measured by ¹³ C-NMR as shown in Examples described later.

The propylene-based resin (A) may contain, in addition to the propylene-derived structural unit and the ethylene-derived structural unit, another structural unit, preferably an α-olefin-derived structural unit having 4 to 20 carbon atoms. The other structural units that can be contained in the propylene-based resin (A) may be one kind or two or more kinds.
The other structural unit that can be contained in the propylene-based resin (A) is preferably 0 to 4% by mass.

The melting point of the propylene resin (A) measured by DSC is 135 to 150 ° C, preferably 136 to 145 ° C.
By using the propylene-based resin (A) having a melting point in the above range, it has an excellent balance of heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher, and is particularly heat resistant and transparent. It is possible to easily obtain a container that is excellent in quality and hardly deformed even after high temperature sterilization.
If the melting point is less than 135 ° C., the heat resistance and blocking resistance of the obtained container are lowered, and the container is likely to be deformed after the sterilization treatment at 121 ° C. or higher. When the melting point exceeds 150 ° C., the impact resistance of the obtained container is lowered, and the transparency is likely to be lowered after the sterilization treatment at 121 ° C. or higher.
Specifically, the melting point can be measured by the method described in the following Examples.

The Rockwell hardness of the propylene resin (A) measured based on JIS K7202 is 65 to 90, preferably 70 to 90, and more preferably 70 to 85.
By using the propylene resin (A) whose Rockwell hardness is in the above range, it is easy to create a container with a good balance of heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization at 121 ° C or higher. Obtainable.

The method for producing the propylene-based resin (A) is not particularly limited as long as a resin satisfying the above requirements (a1) to (a4) can be obtained, but a polymerization method using hydrogen gas as a chain transfer agent in the presence of a catalyst. Is preferable.
As the catalyst, a catalyst containing a metallocene compound, a Ziegler-Natta catalyst, or the like can be used, but a propylene-based resin (A) containing a propylene homopolymerization component having excellent stereoregularity can be easily obtained. It is preferable to use a Ziegler-Natta catalyst.
As the Ziegler-Natta catalyst, various known catalysts can be used, and specifically, for example, (a) a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor, and (b). ) A catalyst containing an organometallic compound catalyst component and (c) an organosilicon compound catalyst component can be used.

The resin composition contains 57 to 75% by mass of the propylene-based resin (A) with respect to 100% by mass of the total of the propylene-based resin (A), the ethylene-based resin (B) and the propylene-based elastomer resin (C). It preferably contains 62 to 75% by mass.
When the content of the propylene resin (A) is within the above range, the heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher are well-balanced, and particularly the blocking resistance and flexibility. It is possible to easily obtain a container that is excellent in quality and is not easily deformed even after high temperature sterilization.
When the content of the propylene-based resin (A) is less than 57% by mass, the obtained container has poor blocking resistance and is liable to be deformed after high-temperature sterilization. If the content of the propylene-based resin (A) exceeds 75% by mass, the obtained container is inferior in flexibility. Changes may occur.

<Ethylene resin (B)>
The ethylene resin (B) is not particularly limited as long as it satisfies all of the above requirements (b1) to (b3).
The resin composition may contain two or more kinds of ethylene resins (B).

The MFR of the ethylene resin (B) at 190 ° C. under a load of 2.16 kg is 0.3 to 3.0 g / 10 minutes, preferably 0.5 g / 10 minutes or more, and preferably 2.5 g / min. It is less than 10 minutes.
When the MFR is in the above range, a resin composition having excellent moldability can be easily obtained.
If the MFR is less than 0.3 g / 10 minutes, the extrudability of the resin composition may deteriorate, and if it exceeds 3.0 g / 10 minutes, drawdown is likely to occur during blow molding.
The MFR can be measured by a method based on JIS K7210.

The density of the ethylene resin (B) is 890 to 915 kg / m ³ , preferably 895 to 915 kg / m ³ , and more preferably 895 to 910 kg / m ³ .
By using the ethylene resin (B) whose density is in the above range, it has an excellent balance of heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C or higher, and is particularly transparent and blocking resistant. A container having excellent properties and impact resistance can be easily obtained.
If the density of the ethylene resin (B) is lower than the above range, the transparency and blocking resistance of the obtained container may be deteriorated, and if it is higher than the above range, the transparency and impact resistance of the obtained container may be deteriorated. May be done.
Specifically, the melting point can be measured by the method described in the following Examples.

The molecular weight distribution (Mw / Mn) obtained by measuring the ethylene resin (B) by GPC is 3.5 or less, preferably 3.0 or less, and more preferably 1.5 to 3.0. ..
By using an ethylene resin (B) having a molecular weight distribution in the above range, it is possible to easily obtain a container having a good balance of heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization at 121 ° C. or higher. Can be done.
Specifically, the molecular weight distribution can be measured and calculated by the method described in the following Examples.

The ethylene-based resin (B) is not particularly limited as long as it satisfies all of the above requirements (b1) to (b3), but is an ethylene / α-olefin copolymer of ethylene and, in particular, an α-olefin having 4 or more carbon atoms. Is preferable.
As the α-olefin, an α-olefin having 4 to 20 carbon atoms is more preferable, an α-olefin having 4 to 10 carbon atoms is further preferable, and 1-hexene is particularly preferable.
The content of the constituent unit derived from α-olefin in the ethylene / α-olefin copolymer is preferably 6 to 20% by mass.

The ethylene-based resin (B) is not particularly limited as long as it is a resin that satisfies the above requirements (b1) to (b3), and may be synthesized by a conventionally known method, and a commercially available ethylene-based polymer is used. You may.
The ethylene resin (B) may be obtained by combining two or more kinds of ethylene polymers to simultaneously satisfy the above requirements (b1) to (b3).

The resin composition contains 10 to 25% by mass of the ethylene resin (B) with respect to 100% by mass of the total of the propylene resin (A), the ethylene resin (B) and the propylene elastomer resin (C). It preferably contains 15 to 25% by mass.
When the content of the ethylene resin (B) is within the above range, the heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher are well-balanced, and particularly impact resistance and flexibility. It is possible to easily obtain a container that is excellent in quality and hardly deformed even after high temperature sterilization.
When the content of the ethylene resin (B) is less than 10% by mass, the impact resistance and flexibility of the obtained container are deteriorated. When the content of the ethylene resin (B) exceeds 25% by mass, the obtained container is liable to be deformed after high temperature sterilization.

<Propene-based elastomer resin (C)>
The propylene-based elastomer resin (C) has a constituent unit derived from propylene of 50 mol% or more and a constituent unit derived from α-olefin having 2, 4 to 20 carbon atoms (however, a constituent unit derived from propylene and a constituent unit derived from α-olefin). The total of the units is 100 mol%), and the present invention is not particularly limited as long as all of the above requirements (c1) to (c4) are satisfied.
The α-olefin having 2, 4 to 20 carbon atoms has the same meaning as the α-olefin having 2 to 20 carbon atoms other than propylene.
The resin composition may contain two or more kinds of propylene-based elastomer resins (C).

Examples of the α-olefin having 2, 4 to 20 carbon atoms as a raw material for the propylene-based elastomer resin (C) include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eikosen and the like. The α-olefin may be used alone or in combination of two or more.
As the α-olefin, ethylene and 1-butene are preferable.

The propylene-based elastomer resin (C) is preferably a copolymer containing a propylene-derived structural unit, an ethylene-derived structural unit, and an α-olefin-derived structural unit having 4 to 10 carbon atoms. More preferably, it is a copolymer composed of only three structural units.

The amount of the propylene-derived constituent unit in the propylene-based elastomer resin (C) is 50 mol% with respect to the total of 100 mol% of the propylene-derived constituent unit and the α-olefin-derived constituent unit having 2, 4 to 20 carbon atoms. The above is preferably 50 to 99 mol%, and more preferably 60 to 99 mol%.
The content of each structural unit in the propylene-based elastomer resin (C) can be measured using ¹³ C-NMR.

The Shore A hardness of the propylene-based elastomer resin (C) measured based on ASTM D2240 is 65 to 90, preferably 68 or more, and preferably 85 or less.
By using a propylene-based elastomer resin (C) whose Shore A hardness is in the above range, it has an excellent balance of heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C or higher, and is particularly flexible. And a container having excellent blocking resistance can be easily obtained.
If the Shore A hardness is less than 65, the blocking resistance of the container containing the layer made of the resin composition after high temperature sterilization may be deteriorated, and if it exceeds 90, the flexibility may be deteriorated. ..

The Shore A hardness was determined by molding a propylene-based elastomer resin (C) under the following press molding conditions to obtain a press sheet having a thickness of 2 mm, and allowing the obtained press sheet to stand at 23 ° C. for 72 hours. It is the value of the scale (based on ASTM D2240) immediately after two press sheets after standing still are stacked and the push needle of the rubber hardness tester (Shore A type) is brought into contact with the stack.
Press molding conditions: temperature; 190 ° C, heating / pressurizing time; 7 minutes, cooling; 15 ° C chiller

The melting point of the propylene-based elastomer resin (C) is 130 to 170 ° C, preferably 135 to 165 ° C.
By using the propylene-based elastomer resin (C) having a melting point in the above range, it has an excellent balance of heat resistance, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher, and is particularly excellent in heat resistance and high temperature sterilization. It is possible to easily obtain a container that is unlikely to be deformed later.

The melting point of the propylene-based elastomer resin (C) is about 10 mg packed in an aluminum pan, (i) heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 5 minutes, and then (ii) 10 ° C./min. It is the temperature of the endothermic peak observed in (iii) when the temperature is lowered to −150 ° C. and then raised to 200 ° C. at (iii) 10 ° C./min.
When there are a plurality of endothermic peaks, the temperature of the endothermic peak at which the height of the peak is maximum is the melting point.

The density of the propylene-based elastomer resin (C) is 860 to 875 kg / m ³ , preferably 860 to 872 kg / m ³ .
By using the propylene-based elastomer resin (C) whose density is in the above range, it has an excellent balance of heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher, and is particularly transparent and flexible. A container having excellent properties and impact resistance can be easily obtained.

The density of the propylene-based elastomer resin (C) is a value measured by a method according to ASTM D1505 after allowing the press sheet obtained in the same manner as for measuring the Shore A hardness to stand at 23 ° C. for 72 hours. Is.

The glass transition temperature (Tg) of the propylene-based elastomer resin (C) measured by DSC is −25 to −35 ° C., preferably −26 to −33 ° C.
By using the propylene-based elastomer resin (C) having a Tg in the above range, a container having excellent flexibility and impact resistance can be easily obtained.

About 10 mg of the propylene-based elastomer resin (C) is packed in a special aluminum pan, the temperature of the Tg is raised from 30 ° C. to 200 ° C. at 200 ° C./min, and the Tg is held at 200 ° C. for 5 minutes, and then (ii). ) DSC obtained at (iii) when the temperature is lowered from 200 ° C. to -100 ° C. at 10 ° C./min, held at -100 ° C. for 5 minutes, and then (iii) is heated at 10 ° C./min. It is a value obtained from a curve.
In the examples, DSCRDC220 manufactured by Seiko Instruments Co., Ltd. was used.

The propylene-based elastomer resin (C) preferably satisfies the above requirements (c1) to (c4) and also satisfies one of the following requirements (c5) and (c6), and both of the following requirements (c5) and (c6) are satisfied. It is more preferable to meet.

(C5): Haze (internal haze) is less than 15%.
The haze is preferably less than 10%.
By using the propylene-based elastomer resin (C) whose haze is in the above range, a container having particularly excellent transparency can be easily obtained.

The haze (internal haze) is a digital turbidity manufactured by Nippon Denshoku Kogyo Co., Ltd. after the press sheet obtained in the same manner as when measuring the Shore A hardness is allowed to stand at 23 ° C. for 72 hours. Using a meter (NDH-2000), the diffuse transmitted light amount by the C light source and the total transmitted light amount by the C light source were measured in the cyclohexanol solution, and the values were calculated by the following formulas.
Haze (%) = 100 x (diffused transmitted light amount) / (total transmitted light amount)

(C6): MFR (measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238) is 3 to 15 g / 10 minutes.
The MFR is preferably 5 to 10 g / 10 minutes.
When the MFR is in the above range, a resin composition having excellent moldability can be easily obtained.

The propylene-based elastomer resin (C) is not particularly limited as long as it is a resin satisfying the above requirements (c1) to (c4), and may be synthesized by a conventionally known method, and a commercially available elastomer may be used. May be good. Examples of the commercially available elastomer include "Toughmer PN" manufactured by Mitsui Chemicals, Inc.

The resin composition contains 10 to 18% by mass of the propylene-based elastomer resin (C) with respect to 100% by mass of the total of the propylene-based resin (A), the ethylene-based resin (B) and the propylene-based elastomer resin (C). , Preferably containing 10 to 15% by mass.
When the content of the propylene-based elastomer resin (C) is within the above range, it is excellent in heat resistance, transparency, impact resistance and blocking resistance that can withstand high temperature sterilization of 121 ° C. or higher, and is particularly excellent in blocking resistance and flexibility. A container having excellent properties can be easily obtained.
When the content of the propylene-based elastomer resin (C) is less than 10% by mass, the flexibility of the obtained container is deteriorated. If the content of the propylene-based elastomer resin (C) exceeds 18% by mass, the blocking resistance of the obtained container deteriorates.

<Various additives>
If necessary, a styrene-based resin may be added to the resin composition as long as the object of the present invention is not impaired. In addition, the resin composition contains various additives such as antioxidants, nucleating agents, lubricants, antiblocking agents, and various synthetic resins used in the synthesis of the resins (A) to (C). It may be contained within a range that does not impair the object of the present invention, and if necessary, these various additives may be blended into the resin composition within a range that does not impair the object of the present invention.

<Preparation method of resin composition>
The resin composition can be prepared by various known production methods. For example, the propylene-based resin (A), the ethylene-based resin (B), and the propylene-based elastomer resin (C) obtained in advance are mixed in the above amounts with various additives as needed, for example, a Henshell mixer. , Ribbon blender, dry blending method using various known devices such as Banbury mixer, and after blending each component in the same manner, various known kneaders such as single-screw extruder, twin-screw extruder, brabender or roll. There is a method of melt-kneading at 170 to 300 ° C., preferably 190 to 250 ° C. using the above.

<Container>
The container is not particularly limited as long as it has at least one layer made of the resin composition.
This container is suitably used for medical and food products, particularly medical use, and particularly preferably for infusion. Specifically, it is suitably used as a container for food packaging represented by a retort pouch, a medical container such as an infusion bag or an infusion bottle, and a container for containing contents that require sterilization under high temperature conditions of 121 ° C or higher. Will be done.

The container may have at least one layer made of the resin composition, and the container made of the single layer (the portion excluding the cap, the tubular member, etc. below is the single layer container) and the layer are 2 A container having more than one layer or a container having a multi-layer structure of the layer and another layer may be used, but the body portion (the portion in contact with the contained material) is made of the resin composition from the viewpoint of simplification during molding and the like. A container having a single layer layer, and further, a container having a single layer layer in which the portion excluding the cap and the tubular member described below is made of the resin composition is preferable.
Even if this container is formed of a single layer in this way, it is less likely to be deformed, blocked, or wrinkled after sterilization at 121 ° C. or higher, and is therefore superior to conventional containers in various respects.

The shape of this container may be arbitrarily selected depending on the intended use of the container, and is not particularly limited, but generally includes a bottle shape, a bag shape, and the like. Further, the molding method of the container is not particularly limited as long as a container having that shape can be obtained, but blow molding, water-cooled inflation molding, air-cooled inflation molding, T-die cast molding and the like are preferable.

This container is preferably used as a container for containing contents that require sterility. The sterilization method is not particularly limited, and a sterilization method required according to the desired container use may be adopted. Even if this container is sterilized at a high temperature, blocking, wrinkles, deformation, etc. do not occur, and it is excellent in heat resistance, transparency, impact resistance, and blocking resistance. Therefore, various methods should be adopted as the sterility method. Can be done.
As the sterilization method, for example, in the case of a container (chemical solution bottle or chemical solution bag) for accommodating an infusion solution such as a chemical solution, usually, the infusion solution is contained in the container, and in a sealed state, high-pressure steam sterilization, hot water shower sterilization, etc. Examples thereof include a known method of performing heat sterilization treatment. In this case, the sterilization treatment temperature can be set to 105 to 121 ° C. according to the type, usage, usage environment and the like of the contents.

This container is sterilized at 121 ° C for 15 minutes at high temperature, and then exposed to ultraviolet light based on the first method of transparency test in "7.02 Plastic Pharmaceutical Container Test Method" described in the 17th revised Japanese Pharmacopoeia. The transmittance of light having a wavelength of 450 nm as measured by the absorbance measurement method is preferably 70% or more, more preferably 75% or more.
If the transmittance after high temperature sterilization treatment at 121 ° C. for 15 minutes satisfies 55% or more, it is considered that the transmittance becomes 55% or more after high temperature sterilization treatment at 116 ° C. for 26 minutes. be able to.

The haze of this container after the sterilization treatment is preferably 50% or less, more preferably 45% or less.
The haze can be measured and calculated according to the method of JIS K7136.

As one aspect of this container, an infusion bottle is preferable, and specific examples thereof include an infusion bottle 10 as shown in FIG.
The infusion bottle 10 shown in FIG. 1 includes a body portion 11, a shoulder portion 12, a neck portion 13, a cap 14, and a hanging portion 15 provided with holes for hanging the infusion solution stand and the like.

In the infusion bottle 10, the portion excluding the cap 14 preferably includes a layer made of the resin composition, and more preferably a single layer.
The hanging portion 15 is preferably configured so as to be foldable when the cap portion is placed face up. Further, after forming a container having no hanging portion, a separately prepared hanging portion may be attached.

When the present container has a bottle shape, the thickness of the body of the container is preferably 0.01 to 1.00 mm, more preferably 0.10 to 0.80 mm.
The thickness of the body portion means an average thickness, and the measurement thereof is obtained by measuring the thicknesses of eight points shown in FIG. 1 (a2) and taking the average value.

When the present container has a bottle shape, the thickness of the neck portion of the container is preferably 0.01 to 5.00 mm, more preferably 1.00 to 3.00 mm.
The thickness of the neck portion is a measurement of the thickness of the central portion C from the base of the cap of the container to the shoulder portion D.

When the present container has a bottle shape, the thickness of the shoulder portion of the container is preferably 0.01 to 2.00 mm, more preferably 0.10 to 1.00 mm.
The thickness of the shoulder portion is a measurement of the thickness of the shoulder portion D of the container.

As another aspect of this container, an infusion bag is preferable, and specific examples thereof include an infusion bag 20 as shown in FIG.
The infusion bag 20 shown in FIG. 2 is provided with a seal portion 22 surrounding the liquid storage portion 21 which is a body portion, and a tubular member 23 for allowing chemicals and the like to flow in and out is engaged with the liquid storage portion 21. A hole 24 for hanging on an infusion stand or the like is provided on the opposite side of the tubular member 23 of the seal portion 22.

In the infusion bag 20, it is preferable that the film constituting the liquid storage portion 21, which is the body portion, includes a layer made of the resin composition.

When the container has a bag shape, the thickness of the body (liquid storage portion) of the container is preferably 0.01 to 1.00 mm, more preferably 0.10 to 0.50 mm, still more preferably 0.15. It is ~ 0.30 mm.
The thickness of the body portion is, for example, the thickness of any 10 points in the 25 regions shown in FIG. 2 (b1), and the average value thereof is taken.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to such Examples.

<Propene resin (A)>
The following PP1 and PP2 were used as the propylene-based resin (A).
"PP1": Propylene resin produced according to Production Example 1 below "PP2": "Prime Polypropylene E111G" manufactured by Prime Polymer Co., Ltd.

[Production Example 1] Production of PP1 (1) Preparation of solid titanium catalyst component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol are reacted at 130 ° C. for 2 hours to prepare a uniform solution. 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
After cooling 75 ml of the uniform solution thus obtained to room temperature, the solution was added dropwise to 200 ml of titanium tetrachloride kept at −20 ° C. over 1 hour. After the charging is completed, the temperature of the obtained mixed solution is raised to 110 ° C. over 4 hours, 5.22 g of diisobutyl phthalate (DIBP) is added when the temperature reaches 110 ° C., and the temperature is kept at the same temperature for another 2 hours. Stirring and holding.
After the reaction for 2 hours was completed, the solid part was collected by hot filtration, the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After the heating is completed, the solid part is collected again by hot filtration and thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound is detected in the liquid to prepare a solid titanium catalyst component. bottom.
The solid titanium catalyst component thus prepared was stored as a hexane slurry, and a part of it was dried to examine the catalyst composition. As a result, the solid titanium catalyst component contained 2.3% by mass of titanium, 61% by mass of chlorine, 19% by mass of magnesium and 12.5% by mass of DIBP.

(2) Prepolymerization catalyst 87.5 g of the solid titanium catalyst component prepared in (1) above, 19.5 mL of triethylaluminum and 10 L of heptane are charged into an autoclave with a stirrer having an internal capacity of 20 L, and the internal temperature is 15 to 20 ° C. 263 g of propylene was charged therein, and the mixture was reacted for 100 minutes with stirring. After completion of the reaction, the solid component was precipitated, the supernatant was removed, and washing with heptane was performed twice to obtain a prepolymerization catalyst. The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted with heptane so that the concentration of the solid titanium catalyst component was 0.7 g / L to obtain a prepolymerization catalyst slurry.

(3) Main Polymerization 300 L of liquefied propylene was charged into a polymerization tank with a stirrer having an internal volume of 500 L, and while maintaining this liquid level, 130 kg / h of liquefied propylene and 0.9 g of prepolymerization catalyst slurry as a solid titanium catalyst component. / H, triethylaluminum 4.9 ml / h, and dicyclopentyldimethoxysilane 8.3 ml / h were continuously supplied and polymerized at 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%.
After deactivating the obtained slurry, it was sent to a washing tank with liquid propylene to wash the copolymer, and then the propylene was evaporated to obtain a powdery propylene / ethylene copolymer (PP1).

Table 1 shows the physical characteristics of the propylene-based resins "PP1" to "PP2". The measuring method of each physical property is as follows.

・ Melt flow rate (MFR: g / 10 minutes)
According to JIS K7210, the measurement was performed under the conditions of 230 ° C. and a 2.16 kg load (kgf).

-Ethylene content (indicated as mass%: mass%)
To measure the content of the building blocks derived from ethylene (ethylene content), 20-30 mg of the sample was dissolved in 0.6 ml of a 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution. Carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed using the resulting solution. The quantification of propylene, ethylene and α-olefin was determined from the diad chain distribution. For example, in the case of a propylene-ethylene copolymer, PP = Sαα, EP = Sαγ + Sαβ, EE = 1/2 (Sβδ + Sδδ) + 1/4 Sγδ, and the following formulas (Eq-1) and (Eq-2) are used. rice field. The unit of ethylene content in this example is expressed in terms of mass%.
Content of constituent units derived from propylene (mol%) = (PP + 1 / 2EP) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)] ... (Eq-1)
Content of building blocks derived from ethylene (mol%) = (1 / 2EP + EE) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)] ... (Eq-2)

The Sαα and the like have peak intensities, and J.I. C. It is a value analyzed according to the method described in Randall (Review Macromolecule Chemistry Physics, C29, 201 (1989)).

-Melting point The melting point of the crystal was determined by measuring under the following measurement conditions using a differential scanning calorimeter (DSC, "Diamond DSC" manufactured by PerkinElmer Co., Ltd.) according to JIS K7121. The apex of the endothermic peak in the third step when the measurement was performed under the following measurement conditions was defined as the melting point. When there are a plurality of endothermic peaks, the apex of the endothermic peak at which the height of the peak is maximum is defined as the melting point.
(Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample amount: 5 mg
Sample shape: Press film (molded at 230 ° C, thickness 400 μm)
Sample pan: Aluminum sample pan with a flat bottom 1st step: Raise the temperature from 30 ° C to 200 ° C at 10 ° C / min and hold for 10 minutes. 2nd step: Lower the temperature to 30 ° C at 10 ° C / min. Step: Raise to 200 ° C at 10 ° C / min

-Rockwell hardness Rockwell hardness was measured on an R scale according to JIS K7202.

<Ethylene resin (B)>
The following PE1 to PE3 were used as the ethylene resin (B).
"PE1": Evolu SP0511, manufactured by Prime Polymer Co., Ltd. "PE2": Evolu SP1022, manufactured by Prime Polymer Co., Ltd. "PE3": Toughmer A-0585X, manufactured by Mitsui Elastomers Singapore

Table 2 shows the physical characteristics of the ethylene resins "PE1" to "PE3" used. The measuring method of each physical property is as follows.

・ Melt flow rate (MFR: g / 10 minutes)
Measured according to JIS K7210 under the conditions of 190 ° C. and 2.16 kg load (kgf).

・ Density [kg / m ³ ]
According to JIS K7112, the strands obtained at the time of MFR measurement were heat-treated at 100 ° C. for 1 hour, left at room temperature for 1 hour, and then measured by the density gradient tube method.

・ Mw / Mn
Using GPC-150C Plus manufactured by Waters, measure the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene as follows, and determine the molecular weight distribution (Mw / Mn) from these values. Calculated.
As the separation column, TSKgel GMH6-HT and TSKgel GMH6-HTL (column size is 7.5 mm inside diameter and 600 mm length, respectively) are used, the column temperature is 140 ° C., and 0.025% by mass is used for the mobile phase. Using o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) containing dibutyl hydroxytoluene (antioxidant, manufactured by Wako Pure Chemical Industries, Ltd.), the flow velocity was 1.0 ml / min, and the sample concentration was 0. The sample injection amount was 500 microliters, and a differential refractive index was used as a detector.
As the standard polystyrene, Tosoh Corporation was used when the molecular weight was Mw <1000 and Mw> 4 × 10 ⁶ , and Pressure Chemical Co., Ltd. was used when 1000 ≦ Mw ≦ 4 × 10 ⁶ .

<Propene-based elastomer resin (C)>
As the propylene-based elastomer resin (C), Toughmer PN3050 manufactured by Mitsui Chemicals, Inc. was used. This propylene-based elastomer resin has a content of 72 mol% of the constituent unit derived from propylene, and contains a constituent unit derived from ethylene and a constituent unit derived from 1-butene as constituent units other than the constituent unit derived from propylene.

The physical characteristics of the shore A hardness (ASTM D2240) are 70, the melting point is 160 ° C, the density (ASTM D1505) is 866 kg / m ³ , the glass transition temperature (Tg) measured by DSC is -29 ° C, and the haze is 6%. , MFR (ASTM D1238) is 6 g / 10 min.
These physical properties are the values measured as described above.

[Example 1] Production of 500 mL bottle The propylene-based resin (A), ethylene-based resin (B) and propylene-based elastomer resin (C) shown in Table 3 are blended in the ratio shown in Table 3, and the total mass of these resins is 100. Antioxidant (Irganox 1010, manufactured by BASF) 500 ppm and Hydrotalcite DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) 400 ppm were added to the portion, and these were added to a twin-screw kneader (Co., Ltd.). ) Kneaded with Kobe Steel Co., Ltd., screw diameter 30 mm) to obtain a resin composition.

The obtained resin composition was subjected to a blow molding machine manufactured by Tahara Co., Ltd. under the conditions of a cylinder temperature of 200 ° C., a die temperature of 200 ° C., and a mold temperature of 15 ° C., and the average thickness of the body was about 0.5 mm. Hollow molding (bottle) was performed so that the average thickness of the neck portion was about 2.0 mm and the average thickness of the shoulder portion was about 0.7 mm. The bottle has an elliptical shape of L84 × W61 × H147 in the shape of the body, specifically the cross section of AA in FIG. 1 (a1), and the shape of the neck, specifically in FIG. 1 (a1). The shape of the cross section of the C portion of the above was a perfect circle shape of Φ21 × H19.

The average thickness of the body is an average value obtained by measuring the thickness of eight points shown in FIG. 1 (a2) of the body of the bottle after sterilization using a Magna-Mike 8500 manufactured by Olympus Corporation.
The average thickness of the neck was measured by measuring the thickness of the central portion C (FIG. 1 (a1)) from the base of the cap of the bottle after the sterilization treatment to the shoulder D using a Magna-Mike 8500 manufactured by Olympus Corporation. It is an average value.
The average thickness of the shoulder portion is an average value obtained by measuring the thickness of the shoulder portion D (FIG. 1 (a1)) of the bottle after the sterilization treatment using a Magna-Mike 8500 manufactured by Olympus Corporation.

[Examples 2 to 6 and Comparative Examples 1 to 4 ] Production of 500 mL Bottle The propylene-based resin (A), ethylene-based resin (B) and propylene-based elastomer resin (C) shown in Table 3 are blended in the ratio shown in Table 3. However, for a total of 100 parts by mass of these resins, an antioxidant (Irganox 1010, manufactured by BASF) 500 ppm, a nucleating agent (Adecastab NA-11, ADEKA Co., Ltd.) 50 ppm, and hydrotalcite DHT-4A. A resin composition was obtained by adding 400 ppm (manufactured by Kyowa Chemical Industry Co., Ltd.) and kneading them with a twin-screw kneader (manufactured by Kobe Steel Co., Ltd., screw diameter 30 mm).
A bottle was produced in the same manner as in Example 1 except that the obtained resin composition was used.

<Tension modulus>
Test pieces were prepared according to ISO295 from the resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 , and measured according to JIS K7161.

<Charpy impact strength>
Test pieces were prepared from the resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 according to ISO295, and measured at 0 ° C. according to JIS K7111.

<Sterilization>
The obtained bottle is filled with 500 mL of distilled water, plugged, and then sterilized at a sterilization temperature of 121 ° C. for 15 minutes using a hot water spray type sterilizer manufactured by Nisaka Seisakusho Co., Ltd., and then at room temperature. Cooled down to.

<Appearance evaluation>
The appearance of the bottle after the sterilization treatment was visually evaluated according to the following items.
◯: Deformation and wrinkles after sterilization did not change in the neck, shoulders and body from before sterilization ×: Deformation or wrinkles were observed in any of the neck, shoulders and body after sterilization.

<Blocking>
The sticky feel of the body of the bottle after the sterilization treatment was evaluated according to the following criteria.
○: No stickiness is felt ×: Stickiness is felt

<Haze>
A test piece was prepared from the body of the bottle after the sterilization treatment according to JIS K7136, and the test piece was measured and calculated according to the method of JIS K7136 using the test piece. The haze was converted and evaluated based on the measured average thickness.

<Transmittance with a wavelength of 450 nm>
Using the bottles before and after the sterilization treatment, the transmittance of light having a wavelength of 450 nm was measured by an ultraviolet-visible absorbance measurement method based on the first method of transparency test described in the 17th revised Japanese Pharmacopoeia.
Specifically, a test piece having a length of 5 cm and a width of 5 cm was cut from the vicinity of the center of the body of each of the bottles before and after the sterilization treatment (16 in FIG. 1 (a1)), and the cut test piece was submerged in water. ) Using UV-1800 manufactured by Shimadzu Corporation, the transmittance of light with a wavelength of 450 nm was measured in the regions of 5 cm in length × 0.9 cm in width and 5 cm in length × 0.9 cm in width at the left and right ends of the test piece. The average value was calculated. The transmittance was converted and evaluated based on the measured average thickness.

10: Infusion bottle 11: Body 12: Shoulder 13: Neck 14: Cap 15: Suspension 16: Underwater light transmittance measurement point 20: Infusion bag 21: Body (liquid storage)
22: Seal part 23: Cylinder member 24: Hole

Claims (6)

Propylene-based resin (A) 57 to 75% by mass satisfying the following requirements (a1) to (a4), and
Ethylene resin (B) 10 to 25% by mass satisfying the following requirements (b1) to (b3),
50 mol% or more of the propylene-derived structural unit and the α-olefin-derived structural unit having 2, 4 to 20 carbon atoms (however, the total of the propylene-derived structural unit and the α-olefin-derived structural unit is 100 mol%. ), And 10 to 18% by mass of the propylene-based elastomer resin (C) satisfying the following requirements (c1) to (c4).
(However, the total of (A) to (C) is 100% by mass), a container containing a layer made of a resin composition.
(A1) MFR at 230 ° C. under a load of 2.16 kg for 0.3 to 5.0 g / 10 minutes (a2) Ethylene content is 3.0 to 8.0% by mass.
(A3) The melting point measured by DSC is 135 to 150 ° C.
(A4) Rockwell hardness (JIS K7202) is 65 to 90.
(B1) MFR at 190 ° C. under a load of 2.16 kg for 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 3.5 or less. (C1) Shore A hardness (ASTM D2240) is 65 to 90.
(C2) Melting point is 130-170 ° C.
(C3) Density (ASTM D1505) is 860-875 kg / m ³
(C4) The glass transition temperature measured by DSC is -25 to -35 ° C. After high-temperature sterilization at 121 ° C. for 15 minutes, the transmittance of light at a wavelength of 450 nm by the ultraviolet-visible absorbance measurement method based on the 17th revised Japanese Pharmacopoeia transparency test method 1 is 70% or more. The container according to claim 1. The container according to claim 1 or 2, wherein the average thickness of the body of the container is 0.01 to 1.0 mm. The container according to any one of claims 1 to 3, wherein the body of the container is a single layer. The container according to any one of claims 1 to 4, which is for medical use or food use. The container according to any one of claims 1 to 5, which is for infusion.

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