JP5144573B2 - Polypropylene resin composition for medical containers and medical containers - Google Patents

Description

  The present invention relates to a polypropylene resin composition for medical containers and a medical container using the same.

Glass containers, plastic bags, and the like are used as containers for chemicals to be injected into the body such as infusions. The glass bottle has a problem that it is heavy and easily broken due to impact or dropping during transportation. At present, plastic containers made of materials such as polyethylene and polypropylene have been used as medical containers.
A medical container using a medical plastic container is formed into a sheet shape or a tube shape by a T-die method or an inflation method, and then a bag-shaped container body is formed by heat fusion or the like, and a chemical solution is filled from an opening. The opening is hermetically sealed and sterilized by steam sterilization or the like.
Polyethylene is inferior in heat resistance, and steam sterilization at 120 ° C. is difficult, so it must be sterilized at a low temperature. Polypropylene is superior to other materials in that steam sterilization at 120 ° C. is possible, but it is inferior in impact resistance at low temperatures, and in particular, the seal part formed by heat fusion is largely peeled off. There was a problem that it was likely to occur when subjected to an impact. Furthermore, the conventional bag material has a problem of low transparency and poor visibility.
In medical containers, flexibility is required to improve drainage, transparency to confirm the contents, drop resistance to prevent destruction during use and transportation, and low temperature Impact resistance is required. Furthermore, the molding stability when molding the container sheet is also a necessary matter. In view of such conditions, a polypropylene resin composition containing a styrenic thermoplastic elastomer having high flexibility and impact resistance and excellent transparency has been proposed.

One applicant of the present application has proposed the following medical containers using a polypropylene resin composition.
In Japanese Patent No. 4016049 (Patent Document 1), a medical multi-chamber container partitioned into a plurality of storage chambers, the inner wall surface of which is from a polymer composition of a crystalline polypropylene polymer and a styrene thermoplastic elastomer. Proposes what will be.
Further, in Japanese Patent No. 3977033 (Patent Document 2), a crystalline polypropylene random copolymer (A) having a flexural modulus of 6000 to 9000 kg / cm ² mainly composed of an isotactic crystalline homopolymer and ethylene-α. -A pharmaceutical liquid container having an inner wall surface of a polymer composition with an ethylene-butene-1 copolymer (B) having a density of 0.879 to 0.90 g / cm ³ which is an olefin copolymer elastomer is proposed.
Further, in Japanese Patent No. 3949739 (Patent Document 3), a medical multi-chamber container partitioned into a plurality of storage chambers, wherein the medical multi-chamber container includes a crystalline polypropylene polymer, a styrene thermoplastic elastomer, and It has been proposed to consist of a single sheet of polymer composition with an ethylene butene-1-copolymer elastomer.

Furthermore, in patent 4119920 gazette (patent document 4), it is a medical multi-chamber container divided into the some storage chamber, Comprising: The medical multi-chamber container is manufactured with the metallocene catalyst, and melting | fusing point is 128- Polypropylene having a melt flow rate of 2.6 to 3.0, ethylene-propylene copolymer, block (polystyrene-ethylenebutylene copolymer-polystyrene) copolymer, block (polystyrene-ethylenepropylene copolymer-polystyrene) copolymer, block (Polystyrene-ethylenebutylene copolymer-polyethylene) copolymer composition with any thermoplastic elastomer, and the weight ratio of the polypropylene to the thermoplastic elastomer is 85:15 to 65:35. Of the polymer composition It has proposed that consists of over door alone.
Furthermore, as a medical infusion container, in order to prevent administration of the drug solution stored in two chambers in an unmixed state, for example, as disclosed in JP-A-9-327498 (Patent Document 5), One applicant of this application has proposed the multi-chamber container provided with the weak seal part for communication inhibition which divides | segments between the compartment which accommodates.

The other of the applicants of the present application has proposed a propylene-based resin composition disclosed in JP-A-2005-248156 (Patent Document 6).
This resin composition is a resin composition containing propylene-ethylene random block copolymer component (A) 35 to 90 wt% and ethylene-α-olefin copolymer component (B) 65 to 10 wt%. Propylene-ethylene, wherein A) satisfies the following conditions (Ai) to (A-ii) and component (B) satisfies the following conditions (Bi) to (B-iv): It is a resin composition by a random block copolymer.
(Ai) 30 to 70 wt% of propylene-ethylene random copolymer component (A1) having propylene alone or ethylene content of 7 wt% or less in the first step using the metallocene catalyst, and component (A1) in the second step It is a propylene-ethylene random block copolymer obtained by sequential polymerization of 70-30 wt% of propylene-ethylene random copolymer component (A2) containing 5-20 wt% more ethylene than (A- ii) In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), the tan δ curve has a single peak at 0 ° C. or less (Bi) produced using a metallocene catalyst. It is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and the ethylene content is 95 to 60 wt% and the content of the α-olefin. It is 5 to 40 wt% refractive index of (B-ii) the density is ^{0.870~0.915g / cm 3 (B-iii} ) a refractive index of component (A) with respect to, the ± 0.007 It is in the range (B-iv) The melt flow rate (190 ° C., 21.18 N load) is 0.1 to 100 g / 10 minutes. Further, JP 2006-307072 A (Patent Document 7) discloses anti-blocking property. A water-cooled inflation molded polypropylene film with improved properties, transparency, flexibility and impact resistance is described. This film is formed by water-cooled inflation molding using a propylene-ethylene block copolymer satisfying the following conditions (Ai) to (A-iii) as a raw material.
(Ai) 30 to 95 wt% of propylene-ethylene random copolymer component (A1) having propylene alone or ethylene content of 7 wt% or less in the first step using the metallocene catalyst, and component (A1) in the second step It is a propylene-ethylene block copolymer (A) obtained by successively polymerizing 70 to 5 wt% of a propylene-ethylene random copolymer component (A2) containing 3 to 20 wt% more ethylene than ( A-ii) Melt flow rate (MFR: 230 ° C. 2.16 kg) is in the range of 1 to 20 g / 10 minutes (A-iii) Temperature-loss tangent (tan δ) obtained by solid viscoelasticity measurement (DMA) In the curve, the tan δ curve has a single peak at 0 ° C. or lower. Although the above has a sufficient effect, the styrenic thermoplastic elastomer Without oxygen, oxygen permeability, moisture permeability is small, transparency and flexibility are required, and even better strength (drop resistance, low temperature impact resistance) and heat sealing properties are required. ing.

Japanese Patent No. 4016049 Japanese Patent No. 3973703 Japanese Patent No. 3949739 Japanese Patent No. 4119920 JP-A-9-327498 JP 2005-248156 A JP 2006-307072 A

As shown in Patent Document 6, the inventors of the present invention have been conducting a series of research and development on a propylene-ethylene block copolymer having a specific component composition produced by multistage polymerization using a metallocene catalyst. Thus, a propylene resin composition having an excellent balance of flexibility, transparency and heat resistance has been found.
And, with this propylene-ethylene block copolymer as the main component, making multifaceted considerations on strength (drop resistance, low temperature impact resistance) and heat seal characteristics, and performing trials from various experiments, the above, The requirements that can solve the problems of the present invention can be newly recognized.
The object of the present invention is to use oxygen-permeable, low moisture permeability, transparency and flexibility without using styrenic thermoplastic elastomer, and even better strength (drop resistance, low temperature impact resistance). The present invention provides a polypropylene resin composition for medical containers having heat sealing properties and a medical container using the same.

What achieves the above object is as follows.
(1) Propylene-based resin component (A) satisfying conditions (Ai) to (A-iii) 50 to 65 wt%, ethylene-α-olefin copolymer satisfying conditions (Bi) to (B-iii) Propylene-based resin composition for medical containers, comprising 25 to 35 wt% of combined component (B) and 10 to 20 wt% of propylene-based resin component (C) satisfying conditions (Ci) to (C-iii) .
-Conditions (Ai) to (A-iii) of the propylene resin component (A)
(Ai) Propylene-ethylene random copolymer component (A1) having a melting peak temperature of 125 to 135 ° C. and an ethylene content of 1.5 to 3.0 wt% in DSC measurement in the first step using a metallocene catalyst. ), And propylene-ethylene random block copolymer obtained by sequential polymerization of propylene-ethylene random copolymer component (A2) having an ethylene content of 8-14 wt% in the second step. Being a polymer (A-ii) Melt flow rate (JIS K7210 A method condition M, 230 ° C. 2.16 kg) is in the range of 4 to 10 g / 10 min. (A-iii) obtained by solid viscoelasticity measurement In the temperature-loss tangent (tan δ) curve, the temperature-loss tangent representing the glass transition observed in the range of −60 to 20 ° C. tan [delta) curve has a single peak, and wherein the single glass transition temperature of 0 ℃ or less, the ethylene -α- olefin copolymer component is a peak of the (B) conditions (B-i) ~ (B-iii)
(B-i) The density is in the range of 0.870 to 0.890 g / cm ³ (B-ii) The melting peak temperature is 80 ° C. or less (B-iii) Melt flow rate (JIS K7210 A method) Condition D, 190 ° C. 2.16 kg) is in the range of 2.0 to 5.0 g / 10 min. Conditions (Ci) to (C-iii) of the propylene resin component (C)
(Ci) 65-75 wt% of a polypropylene component (C1) having a melt flow rate (JIS K7210 A method, condition M, 230 ° C., 2.16 load) in the range of 100 to 200 g / 10 min in the first step, A propylene-ethylene block copolymer obtained by sequentially polymerizing 35-25 wt% of a propylene-ethylene random copolymer component (C2) having an ethylene content of 4-8 wt% and a weight average molecular weight of 800,000-3 million in two steps. (C-ii) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography, is 9.0 to 15 (C-iii) Melt flow rate of the entire propylene resin component (C) (JIS K7210 A method conditions) , 230 ° C., 2.16 load) in the range of 2.0~8.0g / 10min.

Moreover, what achieves the said objective is as follows.
(2) The container body having a drug chamber formed by heat-sealing a sheet formed of the propylene-based resin composition for medical containers according to (1) above, and the lower end of the drug chamber so as to communicate with the container body A medical container having a discharge port heat-sealed to the container body.
(3) The medical container is connected to a container body divided into a first drug chamber and a second drug chamber by a partition part from which an internal space can be peeled, and a discharge communicating with a lower end of the first drug chamber. The medical device according to (2) above, which is a multi-chamber container comprising a port, a first medicine stored in the first medicine chamber, and a second medicine housed in the second medicine chamber container.
(4) The said partition part is a medical container as described in said (3) provided with the center weak seal part and the side part seal part formed in the both sides of this center weak seal part.
(5) The medical container according to (4), wherein the seal strength of the central weak seal portion is lower than the seal strength of the side seal portion.
(6) The medical container according to (3), wherein the multi-compartment container includes a weak seal portion for preventing communication between the first drug chamber and the discharge port.
(7) The medical container according to (6), wherein a seal strength of the weak seal portion for communication inhibition is higher than a seal strength of the central weak seal portion.
(8) The medicine according to any one of (3) to (7), wherein a medicine is stored in each of the first medicine chamber and the second medicine chamber, and at least one medicine is a liquid medicine. Medical container.
(9) The said medical container is what said weak seal part for said communication inhibition peels simultaneously or subsequently with peeling of the said partition part by pressing the chemical | medical agent chamber in which the said liquid agent was accommodated (8). A medical container according to 1.
(10) The medical container according to any one of (6) to (9), wherein the partition part and the weak seal part for communication inhibition are formed by heat sealing.

The polypropylene resin composition for medical containers according to the present invention is mainly composed of a specific propylene-ethylene random block copolymer using a metallocene catalyst, a specific ethylene-α-olefin copolymer and the above propylene. A second propylene-ethylene block copolymer different from the ethylene block copolymer.
By using such a three-component system, without using a styrene-based thermoplastic elastomer, oxygen permeability, moisture permeability is small, transparency and flexibility are provided, and even better strength (drop resistance, It has low-temperature impact resistance) and heat seal properties.
The medical container of the present invention communicates with a container body having a drug chamber formed by heat-sealing a sheet formed of the above-described propylene-based resin composition for a medical container, and a lower end portion of the drug chamber. It has a discharge port heat-sealed in the container body and a medicine stored in the medicine chamber. In particular, by using a sheet formed of the above-described propylene-based resin composition for medical containers, the heat sealability at the seal portion with the discharge port becomes good, and the drop port seal portion has high drop resistance and impact resistance. It will be a thing. In addition, since the container body is made of a sheet formed of the above-described polypropylene resin composition for medical containers, oxygen permeability, moisture permeability is small, under neutral, alkaline and acidic chemical solution filling conditions, Even under high-pressure steam sterilization, the generation of insoluble fine particles is small, and it has transparency and flexibility, and has good strength (drop resistance, low temperature impact resistance).
Further, the medical container communicates with the container main body divided into the first drug chamber and the second drug chamber by the partition weak seal portion from which the internal space can be separated, and the lower end of the first drug chamber. If it is a multi-chamber container comprising a discharge port, a first medicine housed in the first medicine chamber, and a second medicine housed in the second medicine chamber, good heat sealing characteristics It has a partitioning weak seal part.

FIG. 1 is a front view of an embodiment of the medical container of the present invention. FIG. 2 is a graph showing experimental results using the polypropylene resin composition for medical containers of the present invention and the resin composition of Comparative Example.

The polypropylene resin composition for medical containers of the present invention will be described with reference to examples.
The polypropylene-based resin composition for medical containers of the present invention has a propylene-based resin component (A) satisfying the conditions (Ai) to (A-iii) of 50 to 65 wt%, and the conditions (Bi) to (B-iii). ) -Ethylene copolymer component (B) satisfying 25 to 35 wt%, and a propylene resin component (C) satisfying conditions (Ci) to (C-iii) (C) 10 to 20 wt% resin composition It is.

The propylene resin component (A) is a propylene-ethylene random block copolymer and satisfies the following conditions (Ai) to (A-iii).
(Ai) Propylene-ethylene random copolymer component (A1) having a melting peak temperature of 125 to 135 ° C. and an ethylene content of 1.5 to 3.0 wt% in DSC measurement in the first step using a metallocene catalyst. ), And propylene-ethylene random block copolymer obtained by sequential polymerization of propylene-ethylene random copolymer component (A2) having an ethylene content of 8-14 wt% in the second step. Being a polymer (A-ii) Melt flow rate (MFR: JIS K7210 A method condition M, 230 ° C. 2.16 kg) is in the range of 4 to 10 g / 10 min. (A-iii) Solid viscoelasticity measurement In the temperature-loss tangent (tan δ) curve obtained by the above equation, the temperature-loss tangent representing the glass transition observed in the range of −60 to 20 ° C. (Tan [delta) that curve shows the single peak at 0 ℃ below

The propylene resin component (A) will be specifically described.
In the present invention, the propylene-based resin component (A) which is a propylene-ethylene random block copolymer used as a main component of the propylene-based resin composition for medical containers has high transparency, flexibility, and impact resistance. It is a resin provided. The propylene resin composition for medical containers of the present invention is particularly effective as a propylene resin composition for medical multi-chamber containers.

The propylene resin component (A) satisfies the following requirements.
(1) Basic rules The propylene-based resin component (A) uses a metallocene catalyst and has a melting peak temperature Tm (A) in DSC measurement of 125 to 135 ° C in the first step and an ethylene content of 1.5 to 3. 50-60 wt% of the propylene-ethylene random copolymer component (A1) in the range of 0 wt%, and 50-40 wt% of the propylene-ethylene random copolymer component (A2) having an ethylene content of 8-14 wt% in the second step. % Sequential polymerization.

(2) Component (A1) (2-1) Melting peak temperature Tm (A) of component (A1)
The component (A1) produced in the first step is a component that determines crystallinity in the propylene-based resin component (A), and in order for the component (A) to exhibit heat resistance, the component (A1) is melted. The peak temperature Tm (A) needs to be relatively high. However, on the other hand, if Tm (A) is too high, flexibility is insufficient, and in order to control heat seal characteristics, a second propylene-based resin component (a propylene-ethylene random copolymer component described later) ( It is necessary that the difference between the melting peak temperature Tm (C) of C) is large. Therefore, the melting peak temperature Tm (A) of the component (A1) needs to be in the range of 125 to 135 ° C.
That is, when the melting peak temperature Tm (A) is 125 ° C. or lower, the container is likely to be deformed or fused when subjected to high-pressure steam sterilization under chemical filling conditions. Tm (A) needs to be 125 ° C. or higher, preferably 128 ° C. or higher.
On the other hand, when Tm (A) is high, the heat resistance is improved, but not only the flexibility and transparency are easily inhibited, but also the difference from the melting peak temperature Tm (C) of the component (C) is reduced. Therefore, the heat seal curve suddenly rises and it becomes difficult to control multi-stage stable peel strength, so Tm (A) needs to be 135 ° C. or less, preferably 133 ° C. or less. It is.
(2-2) Ethylene content E (A1) of component (A1)
The melting peak temperature Tm (A) of the component (A1) is controlled by the ethylene content, and the ethylene content E (A1) of the component (A1) in the present invention is in the range of 1.5 to 3.0 wt%. When the ethylene content is 1.5 wt% or less, Tm (A) is too high, and when it is 3.0 wt% or more, it is too low.
(2-3) Proportion (A1) of component (A1) in propylene-based resin component (A)
The proportion W (A1) of the component (A1) in the propylene-based resin component (A) is a component that imparts heat resistance to the component (A), but if there is too much W (A1), flexibility and impact resistance May not be sufficient, and transparency may be impaired. Therefore, the ratio of the component (A1) needs to be 60 wt% or less.
On the other hand, if the proportion of the component (A1) becomes too small, the heat resistance is lowered even if the melting peak temperature Tm (A) is sufficient, and the container is deformed when autoclaved under high pressure steam sterilization. And the ratio of the component (A1) must be 50 wt% or more.

(3) About component (A2) (3-1) Ethylene content E (A2) in component (A2)
The propylene-ethylene random copolymer component (A2) produced in the second step is a component necessary for improving the flexibility, impact resistance, and transparency of the propylene-based resin component (A). Generally, in the propylene-ethylene random copolymer, the crystallinity is lowered and the flexibility improving effect is increased by increasing the ethylene content. Therefore, the ethylene content E (A2) in the component (A2) is 8 wt% or more. It is necessary to be. When E (A2) is 8 wt% or less, sufficient flexibility cannot be exhibited, and it is preferably 10 wt% or more.
On the other hand, if the ethylene content is excessively increased to lower the crystallinity of the component (A2), the compatibility between the component (A1) and the component (A2) is reduced, and the component (A2) is not compatible with (A1). To form a domain. In such a phase separation structure, if the refractive index of the matrix and the domain are different, the transparency is drastically lowered. Therefore, the ethylene content of the propylene-ethylene random copolymer component (A2) in the propylene-based resin component (A) used in the present invention needs to be 14 wt% or less, preferably 12 wt% or less.
(3-2) Proportion of component (A2) in propylene-based resin component (A) W (A2)
When the proportion of the component (A2) is too large, the heat resistance is lowered. Therefore, the proportion W (A2) of the component (A2) needs to be suppressed to 50 wt% or less.
On the other hand, since the improvement effect of a softness | flexibility and impact resistance is not acquired when the ratio of a component (A2) becomes too small, the ratio of a component (A2) needs to be 40 wt% or more.

(4) Specific components (A1) and (A2) of ethylene components E (A1) and E (A2) and component amounts W (A1) and W (A2) of components (A1) and (A2) Each ethylene content and component amount are quantified by a material balance at the time of polymerization (material balance) and various known analysis methods. In addition, about the measuring method used in this invention, the detail is described in an Example.

(5) Melt flow rate of propylene resin component (A) MFR (A)
The MFR of the propylene-based resin component (A) needs to be in the range of 4 to 10 g / 10 min.
The melt flow rate MFR (A) of the entire propylene-based resin component (A) is determined by the MFR of each component (A1) and (A2) (referred to as MFR (A1) and MFR (A2), respectively) and the ratio. However, in the present invention, if the overall MFR is in the range of 4 to 10, each MFR is arbitrary as long as the object of the present invention is not impaired. However, when the MFRs of the two are greatly different, an appearance defect or the like may occur. Therefore, both MFR (A1) and MFR (A2) of each component are preferably in the range of 4 to 10 g / 10 min.
If the MFR is low, not only the motor load and the tip pressure increase, but also the problem that the surface of the film becomes rough and the appearance deteriorates, so the MFR needs to be 4 g / 10 min or more, preferably It is 5 g / 10 min or more. On the other hand, if the MFR is too high, the molding tends to be unstable and it is difficult to obtain a uniform film. Therefore, the MFR needs to be 10 g / 10 min or less, preferably 8 g / 10 min or less. is there. In addition, the melt flow rate (MFR) of each resin in the present invention is in accordance with JIS K7210 A method condition M. Test temperature: 230 ° C. Nominal load: 2.16 kg Die shape: Diameter 2.095 mm Length 8.00 mm It is measured.

(6) Specification of glass transition temperature by solid viscoelasticity measurement In the propylene resin component (A), in a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), a range of -60 to 20 ° C. It is necessary that the peak of the tan δ curve representing the glass transition observed in FIG.
When the propylene-based resin component (A) has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A1) is different from the glass transition temperature of the amorphous part contained in the component (A2). , There will be multiple peaks. In this case, there arises a problem that the transparency is remarkably deteriorated. Usually, the glass transition temperature in the propylene-ethylene random copolymer is observed in the range of −60 to 20 ° C., and whether or not the phase separation structure is taken can be determined in the tan δ curve in the solid viscoelasticity measurement in this range, Avoidance of the phase separation structure that affects the transparency of the molded product is brought about by having a single peak below 0 ° C. A specific method of solid viscoelasticity measurement (DMA) is described in Examples.

(7) Manufacturing method of propylene-based resin component (A) The manufacturing method of the propylene-based resin component (A) used in the present invention is a method described in JP-A-2005-248156 and JP-A-4156491. preferable.
Moreover, as a metallocene catalyst, what is disclosed by Unexamined-Japanese-Patent No. 2005-248156 can be used. Representative metallocene compounds include bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (azurenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, ( Cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, Isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylenebis (indenyl) zirconium dichloride, ethylene 1,2-bis (4-phenyl) Nylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene Bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, dimethylsilylenebis {1- (2-methyl-4H-azurenyl)} zirconium dichloride, dimethylsilylenebis [1- {2-methyl -4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride, dimethylsilylenebis {1- (2-ethyl-4-naphthyl-4H-azurenyl)} zirconium dichloride. De, dimethyl gel Mi Len bis (indenyl) zirconium dichloride, dimethyl gel Mi (cyclopentadienyl) (fluorenyl) such as zirconium dichloride can be exemplified. The metallocene catalyst is not limited to the above.

Next, the ethylene-α-olefin copolymer component (B) contained in the propylene resin composition for medical containers of the present invention will be described.
The ethylene-α-olefin copolymer component (B) has the following conditions (Bi) to (B-iii).
(B-i) The density is in the range of 0.870 to 0.890 g / cm ³ (B-ii) The melting peak temperature is 80 ° C. or less (B-iii) Melt flow rate (JIS K7210 A method) Condition D, 190 ° C. 2.16 kg) is in the range of 2.0 to 5.0 g / 10 min. In the present invention, by containing this ethylene-α-olefin copolymer component (B), resin Good impact resistance and heat sealing properties are imparted to the sheet formed using the composition.

Component (B) has the effect of improving the impact strength of the composition at low temperatures. Since the propylene-based resin composition for medical containers in the present invention may be refrigerated during storage or transportation of products, impact resistance at low temperatures is necessary so that no breakage occurs at this time. At this time, if the amount of the component (B) is too small, there arises a problem that not only the heat seal characteristics are sufficient but also the impact resistance is insufficient.
Moreover, the medical container using the propylene-type resin composition for medical containers of this invention is formed by heat-sealing a sheet | seat. Heat sealing is a process in which resin is fused by applying heat and pressure and then cooled and solidified. At this time, the peel strength varies depending on the thickness and shape of the sheet, the seal temperature, the pressure, the time, etc., but in order to control the peel strength, it is important to set a small change in strength with respect to the heat seal temperature. . That is, in the actual heat sealing process, the peel strength is controlled by the temperature of the heating part, but the actual temperature has fluctuations due to disturbances such as errors and ambient temperature, and the change in strength with respect to the heat sealing temperature is abrupt. If it is, peeling strength will change a lot by fluctuation of temperature, and it will be difficult to obtain stable peeling strength. First, the first heat seal characteristic requires a strength range of about 1 to 10 N / 10 mm, preferably 2 to 6 N / min, which is a weak seal strength that can be peeled relatively easily when the container is squeezed by hand. It is to exhibit a weak seal characteristic that allows strength management at a set strength of ± 1 N / 10 mm within a strength range of about 10 mm, and it is important that the influence of the seal strength is small on heat seal temperature fluctuations.

The ethylene-α-olefin copolymer component (B) is poorly compatible with the propylene-based resin components (A) and (C), has a phase separation structure, and has a large difference in melting temperature. Component (B) appears to form domains in propylene-based resin components (A) and (C). Therefore, if the heat seal temperature is such that the propylene resin components (A) and (C) are not melted and heat-sealed, but the component (B) is at a melting temperature, a small proportion of the components in the entire composition Only the portion where (B) is present on the surface is fused, and the weak seal characteristics are controlled by adjusting this amount and the melting temperature in order to show a low fusion strength compared to the whole fusion. It is considered possible.
In addition, when the refractive index of the ethylene-α-olefin copolymer component (B) is significantly different from that of the component (A), the transparency of the composition deteriorates, so it is also important to match the refractive indexes. These melting temperature and refractive index can be controlled by the density, and it is necessary to set the density within a specific range in order to achieve both heat seal characteristics and transparency.

(1) Density For the above reasons, the ethylene-α-olefin copolymer component (B) used in the present invention needs to have a density in the range of 0.870 to 0.890 g / cm ³ .
If the density is too low, the difference in refractive index is increased and the transparency is deteriorated. When the density is less than 0.870, the transparency required for the present invention cannot be ensured and is 0.870 or more. Is necessary, and preferably 0.875 or more.
On the other hand, if the density is too high, the crystallinity becomes high, so that the flexibility, impact resistance and transparency are likely to deteriorate, and the difference between the melting temperature of component (A) and the melting temperature of component (B). When there is no more, it becomes difficult to control the heat seal characteristics, so it is necessary to be 0.890 or less, preferably 0.885 or less.

(2) Melting temperature T (B)
As described above, in order to control the seal strength in a relatively weak heat seal strength region of about 1 to 10 N / 10 mm, it is important to separate the melting temperatures of the component (A) and the component (B). The melting peak temperature T (B) of the component (B) needs to be 80 ° C. or lower. If T (B) is 80 ° C or less, the seal strength can be set within a range of ± 1N / 10mm in the strength region of 1-10N / 10mm, and if T (B) exceeds 80 ° C The heat seal temperature range is narrow, and stable heat seal strength cannot be obtained.

(3) Melt flow rate (JIS K7210 A method condition D, 190 ° C. 2.16 kg)
The resin composition of the present invention needs to have an appropriate fluidity in order to ensure moldability. If the viscosity of the component (B) is too high, the fluidity will be insufficient, resulting in poor dispersion. By doing so, transparency and impact resistance are likely to be reduced, and problems such as variations in heat seal characteristics are likely to occur. Therefore, the ethylene-α-olefin copolymer component (B) in the present invention is required to have a melt flow rate of 2.0 g / 10 min or more, preferably 2.5 or more. On the other hand, if the melt flow rate is too high, the stability during molding is lowered, and it is easy to cause problems such as uneven thickness of the film and reduced impact resistance. Since it melts at a lower temperature than the component (A), if the viscosity is too low, it tends to bleed to the surface due to the heat seal pressure, and the heat seal controllability deteriorates, so the melt flow rate is 5.0 g / 10 min or less. It must be present, and is preferably 4.5 g / 10 min or less.

(4) Ratio of component (B) in resin composition The ratio of component (B) in the resin composition needs to be in the range of 25 to 35 wt%. That is, since the component (B) exists as a domain in the component (A) and has a lower melting temperature than the component (A), only the component (B) melts in a low temperature range, so that the heat seal strength is increased. The low area is controlled. At this time, if the amount of the component (B) is too small, not only the amount of the component (B) present on the film surface decreases, but the strength at the time of weak sealing becomes too low to perform sufficient control, There is a problem that the impact resistance is insufficient and the product is broken during transportation. On the other hand, if the amount is too large, the component (B) is present on the surface in a large amount, which may cause fusion during heat sterilization. The proportion of the component (B) in the present invention in the composition needs to be in the range of 25 to 35 wt%. The impact property becomes insufficient, and when it is 35 wt% or more, the heat resistance is insufficient, so it cannot be used.

(5) Method for Producing Ethylene-α-Olefin Copolymer Component (B) The ethylene-α-olefin copolymer component (B) of the present invention is used to reduce the refractive index difference from the component (A). It is necessary to lower the density, and it is desirable that the crystallinity and molecular weight distribution are narrow in order to suppress stickiness and bleed out. Therefore, it is desirable to use a metallocene catalyst capable of narrowing crystallinity and molecular weight distribution for the production of component (B).
(5-1) Metallocene Catalyst As the metallocene catalyst, various known catalysts used for the polymerization of ethylene-α-olefin copolymers can be used. Specific examples include metallocene catalysts described in JP-A-58-19309, JP-A-59-95292, JP-A-60-35006, and JP-A-3-16388. .
(5-2) Polymerization method As a specific polymerization method, a slurry method, a gas phase fluidized bed method or a solution method in the presence of these catalysts, or a pressure of 200 kg / cm ² or more, a polymerization temperature of 100 ° C. or more. And high pressure bulk polymerization method. A preferable production method includes high-pressure bulk polymerization. The ethylene-α-olefin copolymer component (B) can be appropriately selected from those commercially available as metallocene polyethylene. Examples of commercially available products include DuPont Dow Affinity (registered trademark) and Engage (registered trademark), Nippon Polyethylene Corporation Kernel (registered trademark), Exxon Corporation EXACT (registered trademark), and the like.
In these uses, the density, melting peak temperature, and MFR grade, which are requirements of the present invention, may be selected.
Further, the ethylene-α-olefin copolymer may be a copolymer composed of one kind of α-olefin other than ethylene and ethylene as long as the above conditions (Bi) to (B-iii) are satisfied. And a copolymer comprising two or more α-olefins other than ethylene.

Next, the propylene resin component (C) that is a propylene-ethylene block copolymer contained in the propylene resin composition for medical containers of the present invention will be described.
This propylene-based resin component (C) has the conditions (C-i) to (C-iii).
(Ci) 65-75 wt% of a polypropylene component (C1) having a melt flow rate (JIS K7210 A method, condition M, 230 ° C., 2.16 load) in the range of 100 to 200 g / 10 min in the first step, A propylene-ethylene block copolymer obtained by sequentially polymerizing 35-25 wt% of a propylene-ethylene random copolymer component (C2) having an ethylene content of 4-8 wt% and a weight average molecular weight of 800,000-3 million in two steps. (C-ii) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography, is 9.0 to 15 (C-iii) Melt flow rate of the entire propylene resin component (C) (JIS K7210 A method conditions) , 230 ° C., 2.16 load) in the range of 2.0~8.0g / 10min.

And in this invention, the favorable heat seal characteristic is provided to the sheet | seat formed using the resin composition by containing the propylene-type resin component (C) which is a 2nd propylene-ethylene block copolymer. Yes.
It is desirable that the propylene-based resin composition for medical containers has multi-stage stable peel strength controllability. In the resin composition of the present invention, by containing the component (B) described above, a sealing temperature in a weak seal strength region that is relatively easily peelable, such as about 1 to 10 N / 10 mm, preferably about 2 to 6 N / 10 mm. In contrast, it is possible to exhibit a stable weak seal characteristic. However, it can be easily peeled off, but in addition to the weak seal region of 1 to 10 N / 10 mm, the second heat seal property is higher, about 2 to 25 N / 10 mm, preferably 4 to 20 N, more preferably 6 to It is desirable to control the seal strength in a 15N peel strength region. Further, in order to obtain a product having a stable peel strength, it is necessary to make the change in strength in this region as small as possible with respect to the heat seal temperature as in the case of 1 to 10 N / 10 mm. At this time, in order to manage the strength at a set strength of ± 2 N / 10 mm in an intensity range of 2 to 25 N / 10 mm, it is necessary to improve the propylene resin component itself, and the propylene resin component (C) controls this. It is an ingredient for.
That is, the propylene-based resin component (A) used as the main component in the present invention is manufactured with a metallocene-based catalyst, and thus achieves both high flexibility and transparency, but on the other hand, the crystal of the crystalline component Since the sex distribution is narrow and melts at a specific temperature at one time, the rise in heat seal strength with respect to temperature is rapid. If the distribution of crystallinity is expanded, the higher the crystallinity, the higher the melting temperature, so the heat-sealing strength against temperature will be gentle, but the effect will be sufficient if the melted components easily flow due to the pressure during heat-sealing. Not. At this time, since the propylene-based resin component (A) produced by the metallocene-based catalyst has a narrow molecular weight distribution and does not have a high-molecular weight component, the propylene-based resin component (C) is easily flown by pressure during heat sealing. By containing, the crystallinity distribution is given, and at the same time, the molecular weight is also given a distribution, whereby the change in heat seal strength with respect to the temperature on the high strength side can be made gentle.

(1) Basic rules The propylene-based resin component (C) is a polypropylene component having a melt flow rate (JIS K7210 A method, condition M, 230 ° C., 2.16 load) in the range of 100 to 200 g / 10 min in the first step ( C1) is 65 to 75 wt%, and the propylene-ethylene random copolymer component (C2) having an ethylene content of 4 to 8 wt% and a weight average molecular weight of 80 to 3 million in the second step is sequentially polymerized by 35 to 25 wt%. can get.

(2) About component (C1) Component (C1) is a polypropylene component and is a component with high crystallinity. This component has a higher melting temperature than the component (A) in the composition and is a component for smoothening the change in heat seal strength with respect to the temperature by suppressing fusion at the temperature at which the component (A) melts. . Therefore, the component (C1) needs to have higher crystallinity than the component (A), and is preferably a polypropylene component composed of only propylene.
(2-1) Melt flow rate of component (C1) (JIS K7210 A method, condition M, 230 ° C., 2.16 load)
As will be described later, the component (C2) needs to have a high molecular weight. However, if the molecular weight of the entire component (C) is high, the fluidity is poor and the component cannot be sufficiently dispersed in the composition. Not only is it insufficient, but it also causes uneven flow and poor appearance called gel and fish eye, so it is necessary to ensure the fluidity of the entire component (C) by increasing the fluidity of the component (C1). It is. Therefore, the melt flow rate of the component (C1) needs to be at least 100 g / 10 min. On the other hand, even if the melt flow rate is too high, uneven flow tends to occur, impact resistance and flexibility. Therefore, the melt flow rate of the component (C1) in the present invention needs to be in the range of 100 to 200 g / 10 min.

(3) Component (C2) Component (C2) is a component for suppressing a rapid increase in heat seal strength by lowering the fluidity when the crystal component of component (A) is melted. In order to suppress an increase in heat seal strength by lowering the fluidity, it is necessary that the component (C2) is also melted when the component (A) is melted. Therefore, the component (C2), unlike the component (C1), needs to lower the crystallinity, and the crystallinity is controlled by the ethylene content, so the ethylene content needs to be 4 to 8 wt%. It is.
(3-1) Weight average molecular weight Component (C2) is required to suppress a rapid increase in heat seal strength by inhibiting component (A) from melting and flowing due to heat seal pressure during heat sealing. is there. At this time, if the molecular weight of the component (C2) is low, the effect of inhibiting the flow is insufficient, and the heat seal characteristics cannot be sufficiently improved. Therefore, the component (C2) needs to have a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of 800,000 or more. Further, if the molecular weight becomes too high, the dispersibility deteriorates, so it is necessary to be less than 3 million.
(3-2) Ratio W (C2) of component (C2) in component (C)
Since the component (C2) has a very high molecular weight, if the proportion W (C2) in the component (C) is too large, the component (C) cannot be sufficiently dispersed in the composition, and the heat seal characteristics In addition to not being able to improve the above, it may cause problems such as deterioration of physical properties and poor appearance, so that it is necessary to be 35 wt% or less. On the other hand, if the amount of the component (C2) is too small, the flexibility decreases due to the necessity of a large amount of the component (C) in the composition in order to exhibit sufficient heat sealing properties, and the transparency decreases. Since there is a possibility of incurring, it is necessary to be 25 wt% or more.

(4) The ratio of the component (C) in a composition The ratio for which a component (C) accounts in a composition needs to be the range of 10-20 wt%. In the present invention, the component (C) is a component for improving the heat seal characteristics on the high strength side, and in order to impart a crystallinity distribution to the component (A) and control the melting behavior of the crystal, In order to suppress the flow of the component (C1) and the component (A) due to the pressure at the time of heat sealing, a high molecular weight component (C2) is included, thereby suppressing a rapid increase in heat seal strength with respect to temperature. ing. When the amount of the component (C) is too small, the high crystalline component and the high molecular weight component are insufficient, and a sufficient effect of improving the heat seal characteristics cannot be obtained. Furthermore, the effect of improving sheet formability due to insufficient melt tension cannot be exhibited. On the other hand, when the amount of the component (C) is too large, physical properties such as flexibility and transparency are significantly deteriorated, and the quality required for the resin composition of the present invention cannot be satisfied.
When the ratio of the component (C) in the composition in the present invention is less than 10 wt%, sufficient heat seal characteristics cannot be imparted, so that it is necessary to be 10 wt% or more, preferably 12 wt%. That's it. On the other hand, since physical properties deteriorate at 20 wt% or more, it is necessary to be less than 20 wt%, preferably less than 18 wt%.

(5) About molecular weight distribution (Mw / Mn) which is a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by gel permeation chromatography measurement (GPC) of component (C1). Since the component (C) is composed of the component (C1) and the component (C2) having greatly different molecular weights, the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC). It is necessary that the molecular weight distribution (Mw / Mn) is 9.0 or more. When the molecular weight distribution is less than 9.0, the effect of improving the heat seal characteristics is not sufficient, and when it is 15.0 or more, the dispersibility is deteriorated.

(6) Melt flow rate of component (C1) (JIS K7210 A method, condition M, 230 ° C., 2.16 load) The component (C) used in the present invention contains a component (C2) having a high molecular weight. Nevertheless, sufficient dispersion in the composition is necessary. For this purpose, the component (C) needs to have an appropriate fluidity, and the melt flow rate, which is a measure of fluidity, needs to be in the range of 2.0 to 8.0 g / 10 min. When the melt flow rate is less than 2.0, the dispersion deteriorates, causing not only flow irregularities, gels and fish eyes, but also poor appearance, and heat seal characteristics are difficult to stabilize, and sufficient effects can be obtained. Absent. On the other hand, in the case of 8.0 or more, problems such as physical properties such as impact resistance and a decrease in flexibility occur, and it becomes difficult to obtain the effect of improving the heat seal characteristics.

(7) Production method Component (C) consists of a component (C1) having a low molecular weight and a component (C2) having a very high molecular weight, but these components are extremely different in fluidity, so that both are mixed by melt-kneading. Is virtually impossible. On the other hand, it is not preferable from the viewpoint of cost and environment to blend in a solvent. Therefore, the component (C) used in the present invention must be polymerized and dispersed by sequentially polymerizing the component (C1) in the first step and the component (C2) in the second step.
As the catalyst system for obtaining the component (C), a catalyst mainly composed of a titanium-containing solid catalyst component and an organoaluminum compound, or a metallocene transition metal compound having at least one π-electron conjugated ligand is used. Can do. Here, the component (C2) is preferably produced from a material mainly composed of a titanium-containing solid catalyst component and an organoaluminum compound since the higher the molecular weight component, the greater the effect of improving the heat seal characteristics.

The titanium-containing solid catalyst component is selected from a known supported catalyst component obtained by contacting a solid magnesium compound, titanium tetrahalide and an electron donating compound, and a known catalyst component containing titanium trichloride as a main component. The aluminum compound of the promoter is represented by the general formula AlRnX3 ^-n (wherein R represents a hydrocarbon group having 2 to 10 carbon atoms, and n represents a number of 3 ≧ n> 1.5). When the titanium-containing solid catalyst component is a carrier-supported catalyst component containing a solid magnesium compound, it is preferable to use AlR ³ or a mixture of AlR ³ and AlR ² X, while titanium trichloride or titanium trichloride is mainly used. When the catalyst component is included as a component, it is preferable to use AlR ² X. Furthermore, in the present invention, a known electron donating compound can be used as the third component in addition to the above catalyst and cocatalyst components. The polymerization reaction for obtaining the component (C) can be carried out in the presence of an inert solvent such as hexane or heptane, in the absence thereof, that is, in the presence of liquid propylene or even in gas phase propylene. The reaction can be carried out batchwise using one polymerization tank, or can be carried out continuously by connecting two or more polymerization tanks in series.

The order of the polymerization may be performed in two stages in which the component (C1) is first polymerized and then the component (C2) is polymerized, and additional polymerization may be performed in three stages and four stages.
The catalyst is generally added prior to polymerization in the first stage. Replenishment of the catalyst in the subsequent stage is not necessarily excluded, but it is preferable to add the catalyst in the first stage in order to obtain characteristics that cannot be obtained by resin blending.
In the step (1) for obtaining the component (C1), propylene is polymerized in the presence of hydrogen. Hydrogen is controlled so that the MFR of the polymer obtained in step (1) is in the range of 100 to 200. In general, the hydrogen concentration (in the case of slurry polymerization, the concentration in the gas phase portion, in the polymerization in liquid propylene or in the gas phase method indicates the content in the monomer) is added in an amount of 1 to 50 mol%, preferably 3 to 30 mol%.
The polymerization temperature in step (1) is generally 40 to 90 ° C., and 65 to 75% by weight of the total polymerization amount is produced.
The step (2) for obtaining the component (C2) is polymerization for obtaining a high molecular weight component, and the polymerization is allowed to proceed in a substantially hydrogen-free state with a hydrogen concentration of 0.1 mol% or less. The weight average molecular weight of the polymer obtained in the step (2) is 800,000 to 3,000,000.
The polymerization temperature is usually 40 to 90 ° C., preferably 50 to 80 ° C., and the monomer concentration is controlled so that ethylene is included as a comonomer and the comonomer content is in the range of 4 to 8% by weight.

The propylene-based resin composition for medical containers of the present invention may contain an additional component (additive). As the additive, an antioxidant, a neutralizing agent or the like is used.
Antioxidant is an additive for suppressing thermal stability during molding processing of the resin composition and thermal deterioration of the molded body, and it is necessary to use an additive that has little influence on the contents. Preference is given to tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, octadecyl-3- (3,5-di-) as phenolic antioxidants. It is preferable to avoid t-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-t-butylphenyl) phosphite as a phosphorus-based antioxidant, and those that are easily hydrolyzed. The addition amount is preferably the minimum necessary for ensuring the stability of the resin composition, and is preferably suppressed to 2000 ppm or less. As the neutralizing agent, calcium stearate can be used, but it may cause insoluble fine particles to be generated even after high-pressure steam sterilization depending on the contents, and therefore the addition amount is desirably 200 ppm or less.

Next, the medical container of this invention is demonstrated using the Example shown on drawing.
FIG. 1 is a front view of an embodiment of the medical container of the present invention. In addition, the upper side in the figure is described as “upper end” and the lower side is described as “lower end”.
The medical container 1 according to the present invention is a container that communicates with a container body having a drug chamber formed by heat-sealing a sheet formed of the above-described propylene-based resin composition for a medical container, and a lower end of the drug chamber. And a discharge port heat sealed to the body. The medical container 1 of the present invention may be a medicine-filled medical container having a medicine stored in a medicine chamber.
In particular, the medical container 1 of the illustrated embodiment is a medical multi-chamber container. As a medical container using the propylene-based resin composition for medical containers of the present invention, it is effective to use a medical multi-chamber container, but a single-chamber medical container may be used.

The medical container 1 of this embodiment is made of a flexible material, and is a container main body (soft bag) divided into a first drug chamber 21 and a second drug chamber 22 by a partitioning portion 9 whose internal space can be peeled off. ) 2, the discharge port 3 communicating with the lower end of the first drug chamber 21, the first drug stored in the first drug chamber 21, and the second drug stored in the second drug chamber 22 With drugs. Furthermore, the medical container 1 of this embodiment includes a detachable communication inhibiting portion 10 that inhibits communication between the first drug chamber 21 and the discharge port 3.
As illustrated in FIG. 1, the medical container 1 includes a soft bag 2, a first medicine, a second medicine, a discharge port 3, and a mixed injection port 4.

In addition, as shown in FIG. 1, the soft bag 2 of the present invention includes a first drug chamber 21, a second drug chamber 22, a partition portion 9, a communication inhibition portion 10, a discharge port attachment portion 27, A mixed injection port mounting portion 28 and a medicine injection portion 29 are provided.
The flexible bag 2 is preferably formed into a cylindrical shape by an inflation molding method. The soft bag 2 may be manufactured by various methods such as a blow molding method. Also, the soft bag 2 has a cylindrical body sealed at the entire outer periphery, only the upper and lower ends are sealed, one sheet is folded in half, and the folded portion (side portion 7 or 8) is not included. It may be a bag-like object such as one sealed on the three sides.
That is, the upper end side seal portion 5 and the lower end side seal portion 6 are provided at the upper end portion and the lower end portion of the soft bag 2. The upper end side seal portion 5 and the lower end side seal portion 6 are wide and strong seal portions. Moreover, the side parts 7 and 8 which are strong seal parts may be provided in the side of the soft bag 2. FIG. Further, as shown in FIG. 1, a discharge port mounting portion 27 for mounting the discharge port 3 and a drug injection for injecting a drug into the first drug chamber 21 are inserted into the lower end side seal portion 6 of the soft bag 2. A portion 29 is provided. The discharge port attaching portion 27 and the drug injecting portion 29 are non-seal portions in which a part of the lower end side seal portion 6 communicates with the inside and the outside of the soft bag 2. And the chemical | medical agent injection | pouring part 29 is sealed by the seal | sticker part 6a after chemical | medical agent injection | pouring. In addition, although it is preferable that the chemical | medical agent injection | pouring part 29 is provided in the lower end side seal part 6, it may be provided in the side parts 7 and 8, and does not need to be provided. The upper end side seal portion 5 is provided with a mixed injection port attaching portion 28 for attaching a mixed injection port. The mixed injection port mounting portion 28 is a non-seal portion in which a part of the upper end side seal portion 5 communicates with the inside and the outside of the soft bag. Note that the mixed injection port attachment portion 28 is not necessarily provided. A similar non-seal part may be provided at the same position as the medicine injection part in the second medicine chamber. In addition, the injection part of the medicine in the second medicine chamber may be provided in the side parts 7 and 8.

As shown in FIG. 1, the soft bag 2 is divided into a first drug chamber 21 and a second drug chamber 22 by a partitioning portion 9. And in the medical container 1 of this Example, the partition part 9 is formed of the center weak seal part 9a and the side part seal part 9b formed in the both sides part or both sides of the center weak seal part 9a. In the Example of this invention, the partition part 9 is provided so that the whole horizontal direction of the chemical | medical agent chamber of the soft bag 2 may be crossed, as shown in FIG. The central weak seal portion 9a continues between the two side seal portions 9b extending from the side portions (side seal portions) 7 and 8 of the soft bag 2 toward the center of the soft bag 2, respectively. It is provided to connect. The central weak seal portion 9a and the side seal portion 9b are formed by fusing the sheet material of the soft bag 2 so as to be peelable in a strip shape. With such a configuration, only the central weak seal portion 9a is formed near the center of the medicine chamber, and side seal portions 9b are formed on both sides thereof so as to overlap the central weak seal portion 9a. Further, in this embodiment, the side seal portion 9b is wider than the central weak seal portion 9a, and its upper edge is curved toward the upper end side of the soft bag as it goes to the side portion. . For this reason, when the 2nd chemical | medical agent chamber 22 is compressed, the chemical | medical agent in the chemical | medical agent chamber 22 is comprised so that it may go to the center weak seal | sticker part 9a.
In the medical container 1 of this embodiment, the side seal portion 9b is wider than the central weak seal portion 9a, but it may be of the same or narrower width.

The partition part 9 of the embodiment peels off when one of the drug chambers is strongly pressed with a finger or the like (for example, when pressed or squeezed), and the first drug chamber 21 and the second drug chamber 22 are peeled off. Can communicate with each other. Further, the central weak seal portion 9a is easier to peel off than the communication inhibition portion 10 when the second drug chamber 22 is compressed.
Further, the side seal portion 9b of the embodiment is more difficult to peel off than the central weak seal portion 9a and the communication inhibition portion 10.
The peeling strength of the partition portion 9 (the weak central seal portion 9a) was not peeled off by the pressure applied to the soft bag 2 in the form of two-fold packaging during transportation, and the soft bag 2 was strongly pressed with fingers (squeezed) It is preferable that it peels occasionally. The partition portion 9 is preferably formed by fusing the soft bag 2. The fusion is preferably thermal fusion, high frequency fusion, ultrasonic fusion or the like. Since the soft bag 2 has the two drug chambers 21 and 22 divided into the partition portions 9 in this way, drugs of different components can be mixed aseptically in the soft bag 2. Moreover, in the Example shown in FIG. 1, although the partition part 9 is provided linearly with respect to the soft bag 2, it is not limited to this. In the embodiment of the present invention, the partition portion 9 is constituted by the central weak seal portion 9a and the side seal portion 9b, but is not limited to this, and is constituted only by the central weak seal portion 9a. May be. Moreover, it is preferable that the side part seal part 9b does not peel in a normal usage method. The side seal portion 9b is preferably formed by fusing the soft bag 2 by heat fusion, high frequency fusion, ultrasonic fusion, or the like. The side seal portion 9b may be a strong seal portion that cannot be peeled off.

  Specifically, the seal strength (initial peel strength) of the weak seal portion (central weak seal portion) 9a is preferably 1 to 10 N / 10 mm, and particularly preferably 2 to 6 N / 10 mm. If the seal strength is within this range, the central weak seal part will not be accidentally peeled off during transportation or storage, and the work of peeling the central weak seal part is easy. The seal strength (initial peel strength) of the side seal portion is preferably 3N / 10 mm or more, particularly 4N / 10 mm or more. As the difference in seal strength between the central weak seal portion and the side seal portion (initial peel strength difference), the seal strength of the side seal portion is 3 to 3 from the seal strength (initial peel strength) of the central weak seal portion. It is preferably 30 N / 10 mm, particularly 4 to 25 N / 10 mm larger. In this way, when any one of the drug chambers is pressed, it is possible to prevent the entire weak partitioning part for partitioning from being peeled off at once, and to ensure at least peeling from the central weak sealing part. Further, in the medical container of the present invention, as shown in FIG. 2 and described later, the seal strength gradually rises as the heat seal temperature (mold temperature) rises. By appropriately changing, a desired seal strength can be imparted to the heat seal portion.

In the embodiment of the present invention, the side seal portions 9b are formed on both sides of the central weak seal portion 9a, but the side seal portions 9b may not be formed, and the easily peelable central weak seal is not required. The soft bag 2 may be partitioned only by the part 9a. Further, the portion corresponding to the side seal portion 9b may be a strong seal. Note that the same effect as that of the side weak seal 9b can be obtained by notching a portion corresponding to the side seal 9b and forming the soft bag 2 like a gourd.
When the side seal portion 9b is provided, the length of the central weak seal portion 9a (excluding the side seal portion 9b) is preferably 0.2 to 0.8 with respect to the lateral width of the drug chamber. In particular, it is preferably 0.3 to 0.7. Specifically, the length of the central weak seal portion 9a is preferably 70 to 110 mm, particularly 80 to 100 mm when the width is 190 mm, although it depends on the width of the drug chamber. The width of the central weak seal portion 9a is preferably 8 to 20 mm, particularly 10 to 15 mm. The width of the side seal portion 9b is preferably 6 to 50 mm, particularly 8 to 30 mm.
Moreover, as shown in FIG. 1, it is preferable that the partition part 9 is provided in the position which becomes the upper direction of the communication inhibition part 10 mentioned later, especially the vertical direction. Moreover, it is preferable that the side part seal | sticker part 9b is provided in the both sides of the position which becomes the perpendicular direction upper direction of the communication inhibition part 10, as shown in the figure. By providing the partition portion 9 at such a position, when the partition portion 9 is peeled off, the portion where the communication inhibiting portion 10 of the soft bag 2 is formed swells greatly, so that the communication inhibiting portion 10 is easily peeled off. Become.

Note that the side seal portion 9b may be a seal portion that cannot be substantially peeled off. The part corresponding to the side seal part 9b does not necessarily have to be a peelable seal, and the part may be a strong seal part. In addition, the partition part 9 (central weak seal part 9a) does not need to be formed in strip | belt shape. For example, the partition part 9 (central weak seal part 9a) may be formed in V shape, a semicircle shape, and a semi-elliptical shape. Moreover, the partition part 9 (central weak seal part 9a) may become what peels easily by being produced thinly. Further, in this embodiment, since the discharge port 3 and the weak seal portion 10 for inhibiting communication are provided near the center of the lower portion of the soft bag 2, the central weak seal portion 9 a is correspondingly located near the center of the soft bag 2. Is provided. When the discharge port 3 and the weak seal portion 10 for inhibiting communication are provided at positions close to the side of the soft bag 2, the central weak seal portion 9a is also near the center in the lateral direction of the soft bag 2 correspondingly. It is preferable to provide it at a position close to the side side.
The volume ratio between the first drug chamber 21 and the second drug chamber 22 divided by the partition 9 is preferably 1: 1 to 1: 5.
The volume of the first drug chamber 21 of the medical container 1 should be as small as possible. With such a configuration, when the second medicine chamber 22 is compressed (for example, when pressed or squeezed), the weak seal portion 10 for inhibiting communication is easily peeled off with one action.

  The medical container 1 includes a communication inhibition unit 10. In the medical container 1 of this embodiment, the communication inhibiting part is formed by a communication inhibiting seal part. And in the medical container 1 of this Example, the communication inhibition part 10 is formed so that the upper part of the discharge port 3 may be surrounded. A third chamber 23 isolated from the first drug chamber 21 is formed by the communication inhibition unit 10. The third chamber 23 is an empty room. However, the third chamber 23 may contain a predetermined liquid (for example, water for injection or physiological saline). The third chamber 23 may be in a dry state, but may be filled with a small amount of liquid for sterilization. Furthermore, a passage through which a slight amount of moisture such as water vapor passes may be formed in the weak seal portion 10 for inhibiting communication, and may communicate with the first drug chamber 21 at the above level. The weak seal portion 10 for inhibiting communication can be formed by heat sealing (thermal fusion, high frequency fusion, ultrasonic fusion) of the sheet material.

It is preferable that the communication inhibition part 10 is formed at a position below the central weak seal part 9a portion of the partition part 9. By being formed in such a position, when the first drug chamber 21 or the second drug chamber 22 is pressed (for example, when pressed or squeezed), the communication inhibiting unit 10 is peeled off as described above. It becomes easy to do.
In the embodiment shown in FIG. 1, the communication inhibiting portion 10 is formed in an inverted U-shape (in other words, a U-shape) whose legs are open (in other words, a trapezoid whose short side is on the upper side). Further, the communication inhibiting unit 10 may have a triangular shape with the discharge port 3 as a vertex, a triangular shape with the discharge port 3 as a base, a polygonal shape such as a square shape, a substantially semicircular shape, or a substantially semielliptical shape. In addition, when the communication inhibition part 10 has a corner | angular part in an outer periphery, it is preferable that the edge is not formed in a corner | angular part.
The strength for peeling of the communication inhibiting portion 10 is larger than the strength for peeling of the partition weak seal portion (central weak seal portion 9a). Moreover, the weak seal part 10 for communication inhibition is easier to peel off than the side seal part 9b in the embodiment of the present invention.
Moreover, even if the medical container 1 presses the 1st chemical | medical agent chamber 21, the weak seal part 10 for communication inhibition may peel after peeling of the partition part 9 (central weak seal part 9a). Good. If it is such, the 1st chemical | medical agent chamber 21 of the soft bag 2 can be pressed, and the weak seal part 10 for communication inhibition can be peeled with the force of the fluid at the time of peeling of the partition part 9. FIG.

Further, the weak seal portion 10 for inhibiting communication has the same seal strength as that of the weak seal portion for preventing communication, or slightly higher than the seal strength of the partition portion 9 (central weak seal portion 9a). It can be configured by strengthening. The seal strength (initial peel strength) of the weak seal portion for inhibiting communication is 2 to 25 N / 10 mm, preferably 4 to 20 N / 10 mm, and particularly preferably 6 to 15 N / 10 mm. In the medical container of the present invention, as shown in FIG. 2 and described later, the seal strength gradually rises as the heat seal temperature (mold temperature) rises. By appropriately changing, it is possible to give a desired seal strength to the heat seal portion, and it is easy to give a subtle difference in seal strength between the weak seal portion for blocking communication and the partition portion (central weak seal portion). is there.
The seal strength (initial peel strength) of the weak seal portion for inhibiting communication is preferably 2N / 10 mm or more, particularly 4N / 10 mm or more. The difference in seal strength between the central weak seal part and the weak seal part for communication inhibition (initial peel strength difference) cannot be generally described because of the influence of the shape of the container and each seal part. The seal strength of the seal portion is preferably 0.1 to 10 N / 10 mm, particularly 1 to 5 N / 10 mm greater than the seal strength (initial peel strength) of the central weak seal portion.
In this way, when any one of the drug chambers is pressed, the weak seal part for communication inhibition is prevented from being peeled off before the partition part 9, and the peeling from at least the central weak seal part 9a is ensured. It will be a thing.
A specific method for measuring the peel strength can be performed as follows. The measurement value when the medical container was cut into a length of 10 mm in the width direction of the container and the seal portion of each cut piece was peeled off at a tensile speed of 300 mm / min. Average value.
In the medical container 1, the ratio of the lateral length of the central weak seal portion 9a to the length (shortest distance) between the upper end of the weak seal portion 10 for preventing communication and the upper end of the medicine discharge port is 0. It is preferably 2 to 3, more preferably 0.5 to 2. In particular, it is preferably 0.7 to 1.5. Moreover, it is preferable that the width | variety (band width) of the weak seal part 10 for communication inhibition is 2-20 mm, especially 4-12 mm.

As a material for forming such a flexible bag 2, the above-described polypropylene resin composition for medical containers is used. The soft bag 2 may have a single-layer structure (single-layer body) made of the above-described material, or may be a layer made of the above-described polypropylene-based resin composition for medical containers and other materials. A multilayer product composed of layers may be used. In addition, when forming a soft bag with a multilayered object, it is preferable to use so that the layer which consists of a polypropylene resin composition for medical containers may face each other (in other words, it becomes an inner layer).
The thickness of the sheet material constituting the flexible bag 2 is appropriately determined according to the layer configuration and the characteristics of the material used (flexibility, strength, water vapor permeability, heat resistance, etc.), and is not particularly limited. In general, the thickness is preferably about 100 to 550 μm, more preferably about 200 to 400 μm. Further, as the soft bag 2, it is preferable to use an extruded film or a blown tube having a tensile elastic modulus of 500 MPa or less, preferably 50 to 300 MPa.
The soft bag 2 is produced by blow molding using the above resin, formed by fusing the peripheral edges of two sheets formed by the resin, and one sheet formed by the resin. It may be any one that is formed by folding the sheet and fusing the remaining three open edges.

  Drugs are stored in the drug rooms 21 and 22 of the soft bag 2. The chemical chambers 21 and 22 are different in that they coexist with each other, such as precipitation due to coexistence, separation of components that may change over time or coloration / decomposition due to temporary heating, etc. It is preferred that the components are contained. As such a drug (infusion solution), for example, it is necessary to mix two or more drugs at the time of infusion, such as peritoneal dialysis solution, transcentral vein infusion, transperipheral vein injection, liquid nutrient, etc. Some are preferable. Examples of the infusion include physiological saline, electrolyte solution, Ringer's solution, high-calorie infusion, glucose solution, water for injection, amino acid electrolyte solution, and the like, but are not limited thereto. For example, a glucose electrolyte solution is stored in one of the drug rooms and an amino acid solution is stored in the other, and water-soluble vitamins such as vitamin B1, vitamin B2, vitamin B6, vitamin C, panthenol, and nicotinamide are stabilized in both rooms It can be sorted and stored as appropriate in consideration of the properties and the like.

In this medical container 1, the separation portion 9 and the weak seal portion 10 for blocking communication due to the compression of the first drug chamber 21 and the separation portion 9 and the communication blocking effect due to the pressure of the second drug chamber 22 are compressed. There is a difference in the peeling workability of the weak seal portion 10. The superiority or inferiority in the difference in the peeling workability here is a comparison of which one of the drug chambers can be easily peeled off the partition 9 and the weak seal portion 10 for inhibiting communication when both the drug chambers are pressed individually. It is a result.
In the medical container 1 of the present invention, even if the first drug chamber 21 or the second drug chamber 22 is pressed, the partition 9 and the communication blocking unit 10 are peeled in one order in this order. ing. However, in the medical container 1 of the present invention, as described above, the partitioning portion 9 by the compression of the first drug chamber 21 and the separation workability of the communication inhibiting portion 10 and the partitioning portion 9 by the compression of the second drug chamber 22 are performed. And there is a difference in the peeling workability of the communication inhibiting part 10. This is due to the ease of deformation of the medicine chamber, the size of the medicine chamber, the amount of medicine filled in the medicine chamber, and the like. And, the superiority or inferiority of workability is determined as to which of the first drug chamber 21 and the second drug chamber 22 is better when the one-action partitioning portion and the communication inhibiting portion are continuously peelable. The standard.

Further, the upper end side seal portion 5 of the soft bag 2 is provided with a hole (hanging portion) 25 for hanging on a hanger or the like.
As shown in FIG. 1, the discharge port 3 is attached to a discharge port attachment portion 27 formed in the lower end side seal portion 6 of the soft bag 2. The discharge port mounting portion 27 is provided at the center of the lower end side seal portion 6. The medical container 1 also includes a mixed injection port 4 for mixing chemical solutions. By doing in this way, components other than the chemical | medical agent put into the medical container 1 can be mixedly injected before use. The discharge port 3 and the mixed injection port 4 are attached to the soft bag 2 by high frequency fusion, heat fusion, ultrasonic fusion, or the like. As the discharge port 3 and the mixed injection port 4, known ones can be used.

Specific examples of the present invention will be described.
1. Propylene resin component (A) (propylene-ethylene random block copolymer)
(1) Method for measuring physical properties of component (A) (1-1) Melt flow rate MFR (A)
According to JIS K7210 A method condition M, it measured on condition of the following.
Test temperature: 230 ° C
Nominal weight: 2.16kg
Die shape: Diameter 2.095mm Length 8.00mm

(1-2) Specification of each component amount W (A1) and W (A2) (1-2-1) Temperature rising elution fractionation method (TREF)
A technique for evaluating the crystallinity distribution of a propylene-ethylene random copolymer by temperature-elevated elution fractionation (TREF) is well known to those skilled in the art. It is shown.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Po
lym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36,
8, 1639-1654 (1995)
The propylene-based resin component (A) in the present invention has a large difference in crystallinity between the components (A1) and (A2), and each crystallinity distribution is narrow by being produced using a metallocene-based catalyst. Therefore, there are very few intermediate components between the two, and both can be accurately separated by TREF.
Specifically, in the present invention, the measurement is performed as follows. A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Then, a component of -15 ° C o-dichlorobenzene (containing 0.5 mg / ml BHT), which is a solvent, flows through the column at a flow rate of 1 ml / min, and is dissolved in -15 ° C o-dichlorobenzene in the TREF column. Is eluted for 10 minutes, and then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.
In the obtained elution curve, the components (A1) and (A2) show their elution peaks at the respective temperatures T (A1) and T (A2) due to the difference in crystallinity, and the difference is sufficiently large. Separation is possible almost at T (A3) (= {T (A1) + T (A2)} / 2).
Here, if the integrated amount of the component eluted before T (A3) is defined as W (A2) wt%, and the integrated amount of the component eluted at T (A3) or higher is defined as W (A1) wt%, W (A2) Corresponds to the amount of the component (A2), and the integrated amount W (A1) of the component eluted at T (A3) or higher corresponds to the amount of the component (A1) having relatively high crystallinity.
The equipment and specifications used for the measurement are shown below.
(TREF part)
TREF column: 4.3 mmφ x 150 mm stainless steel column Column packing material: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve (sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length: 1.5 mm Window shape: 2φ x 4 mm long circle Synthetic sapphire window measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / ml BHT)
Sample concentration: 5 mg / ml
Sample injection volume: 0.1 ml
Solvent flow rate: 1 ml / min

(1-3) Identification of ethylene content E (A1) and E (A2) in each component The ethylene content E (A1) and E (A2) of each component is a temperature rising column fractionation using a preparative fractionator. Each component is separated by the method, and the ethylene content of each component is determined by NMR.
The temperature rising column fractionation method is a measurement method disclosed in, for example, Macromolecules 21 314-319 (1988). Specifically, the following method was used in the present invention.
(1-3-1) Temperature rising column fractionation A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 ml of a sample o-dichlorobenzene solution (10 mg / ml) dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (A3) (obtained by TREF measurement) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (A3), 800 ml of o-dichlorobenzene of T (A3) is allowed to flow at a flow rate of 20 ml / min, whereby components soluble in T (A3) present in the column are obtained. Elute and collect.
Next, the column temperature is increased to 140 ° C. at a rate of temperature increase of 10 ° C./min, left at 140 ° C. for 1 hour, and then 800 ml of o-dichlorobenzene as a solvent at 140 ° C. is flowed at a flow rate of 20 ml / min. , T (A3) is eluted and recovered.
The polymer-containing solution obtained by fractionation is concentrated to 20 ml using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is collected by filtration and dried overnight in a vacuum dryer.

(1-3-2) Measurement of ethylene content by ¹³ C-NMR The ethylene content of each of the components (A1) and (A2) obtained by the above fractionation was measured according to the following conditions by the proton complete decoupling method. , By analyzing the ¹³ C-NMR spectrum.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (carbon nuclear resonance frequency of 100 MHz or more)
Solvent: o-dichlorobenzene / heavy benzene = 4/1 (volume ratio)
Concentration: 100 mg / ml
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more The attribution of the spectrum may be performed with reference to, for example, Macromolecules 17 1950 (1984). The spectral attributions measured under the above conditions are shown in Table 1. In the table, symbols such as S _αα follow the notation of Carman et al. (Macromolecules 10 536 (1977)), P represents a methyl carbon, S represents a methylene carbon, and T represents a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules 15 1150 (1982) and the like, the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × {I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads.
Therefore, [PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .
By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
Note that the propylene-ethylene random copolymer of the present invention contains a small amount of propylene heterogeneous bonds (2,1-bonds and / or 1,3-bonds), thereby producing the minute peaks shown in Table 2. .

In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content of the present invention is obtained by using the relational expressions (1) to (7) as in the analysis of the copolymer produced with a Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. I will do it.
Conversion from mol% to wt% of ethylene content is performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100 where X is the ethylene content in mol%.

(1-4) Solid viscoelasticity measurement (DMA)
The sample used was cut into a strip of 10 mm width × 18 mm length × 2 mm thickness from a 2 mm thick sheet injection molded under the following conditions. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
[Preparation of specimen]
Standard number: JIS-7152 (ISO294-1)
Molding machine: EC-20 injection molding machine manufactured by Toshiba Machine Molding machine set temperature: 80, 80, 160, 200, 200, 200 ° C from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / sec (speed in the mold cavity)
Holding pressure: 20 MPa
Holding time: 40 seconds Mold shape: Flat plate (thickness 2 mm, width 40 mm, length 80 mm)

(1-5) Melting peak temperature Tm (A)
Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./min, and further melt at a rate of temperature increase of 10 ° C./min. The melting peak temperature was Tm (unit: ° C.).

(2) [Production Example A-1]
(2-1) Preparation of prepolymerization catalyst (2-1-1) Chemical treatment of silicate Into a glass separable flask equipped with a 10-liter stirring blade, 3.75 liters of distilled water, followed by concentrated sulfuric acid (96 %) 2.5 kg was slowly added. At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.
(2-1-2) Drying of silicate The silicate chemically processed previously was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50mm Heating zone 550mm (electric furnace)
Number of revolutions with lifting blade: 2 rpm Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)
(2-1-3) Preparation of catalyst An autoclave having an internal volume of 16 liters having a stirring and temperature control device was sufficiently substituted with nitrogen. 200 g of dry silicate was introduced, 1160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 270 ml of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium and 2,180 mg (0.3 mM) of mixed heptane Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.
(2-1-4) Preliminary polymerization / washing Subsequently, the temperature in the tank was raised by 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5,600 ml of mixed heptane were further added, stirred for 30 minutes at 40 ° C., allowed to stand for 10 minutes, and then 5,600 ml of the supernatant was removed. It was. This operation was further repeated 3 times. When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mM mol / L, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the charged amount Was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.

(2-2) Production of propylene-ethylene block copolymer Using the prepolymerized catalyst prepared as described above, a propylene-ethylene block copolymer was produced according to the following procedure.
(2-2-1) First polymerization step A horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade was sufficiently dried, and the interior was sufficiently replaced with nitrogen gas. While stirring at a rotation speed of 30 rpm in the presence of a polypropylene powder bed, 0.568 g / hr of the prepolymerized catalyst adjusted by the above method (as the amount of solid catalyst excluding the prepolymerized powder) in the upstream part of the reactor, Triisobutylaluminum was continuously fed at 15.0 mmol / hr. The monomer mixed gas is continuously reacted so that the reactor temperature is maintained at 65 ° C., the pressure is maintained at 2.1 MPaG, the ethylene / propylene molar ratio in the reactor gas phase is 0.07, and the hydrogen concentration is 100 ppm. It was made to distribute | circulate in a container and vapor phase polymerization was performed. The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, the amount of the polymer extracted when the steady state was reached was 10.0 kg / hr.
When the propylene-ethylene random copolymer obtained in the first polymerization step was analyzed, the MFR was 6.0 g / 10 min and the ethylene content was 2.2 wt%.
(2-2-2) Second polymerization step The propylene-ethylene copolymer extracted from the first step was continuously supplied to a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade. . While stirring at a rotational speed of 25 rpm, the temperature of the reactor is maintained at 70 ° C., the pressure is maintained at 2.0 MPaG, and the ethylene / propylene molar ratio in the gas phase in the reactor is 0.453, and the hydrogen concentration is 330 ppm. A monomer mixed gas was continuously passed through the reactor to carry out gas phase polymerization. The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer extracted was 17.9 kg / hr, and the polymerization reaction amount in the second polymerization step was controlled. The activity was 31.4 kg / g-catalyst.
Various analysis results of the propylene-ethylene block copolymer PP (A-1) thus obtained are shown in Table 3.

(3) Production Examples A-2 to 9
Except for changing the polymerization conditions as shown in Table 3 and Table 4, catalyst preparation and polymerization were performed in the same manner as in Production Example A-1.
After the reaction was completed, various analyzes of the obtained polymer were performed. Tables 3 and 4 show the results of various analyzes of the obtained propylene-ethylene block copolymers PP (A-2) to (A-9). These satisfy all the requirements of the present invention as component (A).

(4) Production Examples A-10 to 17
Except for changing the polymerization conditions as shown in Table 5 and Table 6, catalyst preparation and polymerization were carried out in the same manner as in Production Example A-1.
After the reaction was completed, various analyzes of the obtained polymer were performed. Tables 5 and 6 show various analysis results of the obtained propylene-ethylene block copolymers PP (A-10) to (A-17). These do not satisfy the requirements of the present invention as component (A).

2. Ethylene-α-olefin copolymer component (B)
(1) Method for measuring physical properties of component (B) (1-1) Melt flow rate MFR (B)
According to JIS K7210 A method condition D, it measured on condition of the following.
Test temperature: 190 ° C
Nominal weight: 2.16kg
Die shape: Diameter 2.095mm Length 8.00mm
(1-2) Density Using the extruded strand obtained at the time of MFR measurement, the density gradient tube method was used in accordance with the JIS-K7112 D method.
(1-3) Melting peak temperature Tm (B)
Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./min, and further melt at a rate of temperature increase of 10 ° C./min. The melting peak temperature was Tm (unit: ° C.).

(2) Production Example of Component (B) (2-1) Production Example B-1
A copolymer of ethylene and hexene-1 was prepared. The catalyst was prepared by the method described in JP-T-7-508545. That is, to the complex dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl 2.0 mmol, tripentafluorophenyl boron was added in an equimolar amount to the above complex, and diluted to 10 liters with toluene. A catalyst solution was prepared.
A mixture of ethylene and 1-hexene was supplied to a stirred autoclave type continuous reactor having an internal volume of 1.5 liter so that the composition of 1-hexene was 73% by weight, and the pressure in the reactor was maintained at 130 MPa. The reaction was performed at 127 ° C. The polymer production per hour was about 2.5 kg.
After the reaction was completed, various analyzes of the obtained polymer were performed. Various analysis results of the obtained ethylene / α-olefin copolymer PE (B-1) are shown in Table 7.
(2-2) Production Examples B-2 to 6
Catalyst preparation and polymerization were carried out in the same manner as in Production Example B-1, except that the composition of 1-hexene and the polymerization temperature during polymerization were changed as shown in Table 7.
After the reaction was completed, various analyzes of the obtained polymer were performed. Table 7 shows various analysis results of the obtained ethylene / α-olefin copolymer (PE-2 to 6).

3. Propylene-based resin component (C) Propylene-ethylene block copolymer (1) Measuring method of physical properties of component (C) (1-1) Melt flow rate MFR (C1), MFR (C)
According to JIS K7210 A method condition M, it measured on condition of the following.
Test temperature: 230 ° C
Nominal weight: 2.16kg
Die shape: Diameter 2.095mm Length 8.00mm

(1-2) Molecular Weight Measurement In the present invention, the molecular weight distribution (Mw / Mn), the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by gel permeation chromatography (GPC). .
Conversion from the retention capacity to the molecular weight in the GPC measurement is performed using a standard curve prepared in advance by standard polystyrene.
Standard polystyrenes used are the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is prepared by injecting 0.2 ml of a solution dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml.
The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical values are used for [η] = K × M ^α in the viscosity formula used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ α = 0.7
PE: K = 3.92 × 10 ⁻⁴ α = 0.733
PP: K = 1.03 × 10 ⁻⁴ α = 0.78
The measurement conditions for GPC are as follows.
Equipment: GPC (ALC / GPC 150C) manufactured by WATERS
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min
Injection volume: 0.2ml
Sample Preparation Prepare a 1 mg / ml solution using o-dichlorobenzene (containing 0.5 mg / ml BHT) and dissolve it at 140 ° C. for about 1 hour.

(1-3) Specification of each component amount W (C1) and W (C2) Component (C) consists of components (C1) and (C2), and the proportion of each component can be determined from the material balance. Since their molecular weights are greatly different from each other, the ratio of each component can be specified by performing peak separation from a plot of the elution ratio with respect to the molecular weight obtained by GPC measurement.
For peak separation, using commercially available calculation software, assuming that each component has a normal distribution, fitting with two components can be performed to determine the proportion of each component and the weight average molecular weight.

(1-4) Ethylene content E (C2) in component (C2)
Component (C) consists of component (C1) that does not contain ethylene and component (C2) that contains ethylene. Therefore, the ethylene content in component (C2) is determined from the ethylene content in component (C) and the ratio of each component. The amount can be calculated.
That is, E (C2) = E (C) × 100 / W (C2)
At this time, ethylene content in a component (C) can be measured by ¹³ C-NMR mentioned above.

(2) Production Example of Component (C) (2-1) Production Example C-1
(2-1-1) Production of solid catalyst component (a) 20 liters of dehydrated and deoxygenated n-heptane and 20 liters of MgCl ₂ were introduced into a tank equipped with a stirrer with an internal volume of 50 liters sufficiently purged with nitrogen. Mole, 20 mol of Ti (On-C ₄ H ₉ ) 4 was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 12 liters of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.
Subsequently, 5 liters of n-heptane purified as described above was introduced into the tank using the tank equipped with a stirrer, and 3 mol of the solid component synthesized above was introduced in terms of Mg atoms. Subsequently, 5 mol of SiCl ₄ was mixed with 2.5 liters of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed.
Next, 2.5 liters of n-heptane was introduced into the tank equipped with a stirrer, 0.3 mol of phthalic acid chloride was mixed, introduced at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 2 liters of TiCl ₄ was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid component (a1) for producing component (a) was obtained by washing with n-heptane. The titanium content of this solid component was 2.0% by weight.
Next, 8 liters of n-heptane, 400 grams of the solid component (a1) synthesized above were introduced into the tank equipped with a stirrer substituted with nitrogen, and 0.6 liter of SiCl ₄ was introduced as the component (a2) at 90 ° C. The reaction was performed for 2 hours. After completion of the reaction, 0.54 mol of (CH ₂ ═CH) Si (CH ₃ ) ₃ was further used as component (a3), and (t—C ₄ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ was used as component (a4). 0.27 mol and 1.5 mol of Al (C ₂ H ₅ ) ₃ as component (a5) were sequentially introduced and contacted at 30 ° C. for 2 hours. After completion of the contact, the product was thoroughly washed with n-heptane to obtain 390 g of component (a) mainly composed of magnesium chloride. The titanium content of this product was 1.8% by weight.

(2-1-2) Polymerization A stainless steel autoclave with a stirrer with an internal volume of 400 liters was sufficiently replaced with propylene gas, and 120 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, 30 g of triethylaluminum, 70 liters of hydrogen, and 10 g of the catalyst a were added under the condition of a temperature of 70 ° C. After the autoclave was heated to an internal temperature of 75 ° C., propylene was supplied at a rate of 21.0 kg / hour and hydrogen was supplied at a rate of 79.8 L / hour to initiate polymerization. After 150 minutes, the introduction of propylene and hydrogen was stopped. The pressure was 0.34 kg / cm ² G at the start of polymerization, increased with time during the supply of propylene, and increased to 5.4 kg / cm ² G when the supply was stopped. Then, after the pressure in the vessel is subjected to residual polymerization until drops to 3.5 kg / cm ² G, and releasing the unreacted gas to 0.3kg / cm ² G. During this time, the polymerization temperature was maintained in the range of 75 ± 1 ° C. (one-stage polymerization).
Next, after setting the autoclave at an internal temperature of 65 ° C., 16.0 cc of n-butanol was introduced, and then propylene was supplied at a rate of 9.4 kg / hour and ethylene was supplied at a rate of 0.6 kg / hour to initiate two-stage polymerization. did. After 135 minutes, the introduction of propylene and ethylene was stopped. The pressure increased with time during the supply of propylene and ethylene, and increased to 4.1 kg / cm ² G when the supply was stopped. Then, after the pressure in the vessel is subjected to residual polymerization until drops to 1.8 kg / cm ² G, releasing the unreacted gas in the vessel up to 0.3kg / cm ² G. During this time, the polymerization temperature was maintained in the range of 65 ± 1 ° C. (two-stage polymerization).
The obtained slurry is transferred to the next tank with a stirrer, 5 liters of butanol is added, treated at 70 ° C. for 3 hours, further transferred to the next tank with a stirrer, and 100 liters of pure water in which 100 g of sodium hydroxide is dissolved. In addition, after treating for 1 hour, the aqueous layer was allowed to stand and then separated to remove the catalyst residue. The slurry was treated with a centrifugal separator to remove heptane, and then treated with a dryer at 80 ° C. for 3 hours to completely remove heptane, thereby obtaining 56.4 kg of a propylene polymer (product).
After the reaction was completed, various analyzes of the obtained polymer were performed. Table 8 shows various analysis results of the obtained propylene-based resin component PP (C-1).

(2-2) Production Examples C-2 to 10
Polymerization was carried out by the same production method as Production Example C-1, except that the polymerization conditions were changed as shown in Tables 8 and 9.
After the reaction was completed, various analyzes of the obtained polymer were performed. Various analysis results of the obtained propylene-based resin components PP (C-2) to (C-10) are shown in Table 8 and Table 9.

Example 1
1. PP (A-1) obtained in Production Example A-1 as the component (A), PE (B-1) obtained in Production Example B-1 as the component (B), and Production Example as Component (C) PP (C-1) obtained in C-1 was weighed to 58, 27, and 15 wt%, respectively, and after being put into a Henschel mixer, this component (A), component (B), and component (C) The following antioxidant and neutralizing agent were added to 100 parts by weight of the mixture, and the mixture was sufficiently stirred and mixed.
Antioxidant: Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Ciba Specialty Chemicals Co., Ltd. Irganox 1010) 0.08 weight Parts, 0.02 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (Irgaphos 168 manufactured by Ciba Specialty Chemicals Co., Ltd.), octadecyl-3- (3,5-di-t-butyl) -4-Hydroxyphenyl) propionate (Irganox 1076 manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.015 parts by weight Neutralizer: Calcium stearate (Ca-St manufactured by Nitto Kasei Kogyo Co., Ltd.) 0.003 parts by weight

2. Granulation In a PCM twin screw extruder manufactured by Ikegai Seisakusho with a screw diameter of 30 mm, the melted resin extruded from the strand die was melted and kneaded in a cooling water tank at a screw rotation speed of 200 rpm, a discharge rate of 10 kg / hr, and an extruder temperature of 190 ° C. The material was taken out while being cooled and solidified, and the strand was cut into a diameter of about 2 mm and a length of about 3 mm using a strand cutter to obtain a propylene-based resin composition raw material pellet.

3. Film physical property evaluation In order to evaluate the basic physical properties of the obtained propylene-based resin composition raw material pellets, from a T-die having a diameter of 30 mm and a L / D = 32 width of 300 mm and a Lip width of 0.5 mm The film was extruded at a set temperature of 200 ° C., cooled with a cooling roll having a roll temperature of 20 ° C. and an air knife, and cast at a speed of 2 m / min to obtain a film having a thickness of 300 μm. The obtained film was conditioned for 24 hours or more in an atmosphere of 23 ° C. and 50% RH.
Next, the two films were cut out to 200 × 200 mm, overlapped and heat-sealed in three directions, filled with about 600 cc of distilled water, and the remaining one was heat-sealed. The obtained bag was autoclaved at 115 ° C. for 30 minutes in an autoclave, and left at 23 ° C. for 24 hours or more, and then drained to obtain a sterilized film. At this time, whether or not the heat resistance was sufficient was visually determined as to whether the film was stuck or not deformed.
The physical properties of the obtained sterilized film were evaluated for the following items. Table 10 shows the evaluation results.

(1) Transparency (HAZE) measurement It measured with the haze meter based on JIS-K7136-2000. The smaller the value obtained, the better the transparency.
(2) Measurement of tensile elastic modulus Based on JIS K-7127-1989, the tensile elastic modulus in the flow direction (MD) of the film was measured under the following conditions.
Sample length: 150mm
Sample width: 15mm
Distance between chucks: 100mm
Crosshead speed: 1mm / min
(3) Tear impact strength Using a mold created so that the obtained film is half the size of a not-cut angle type test piece described in JIS-K6252-2001, the tear direction is perpendicular to the flow ( TD) (test specimen longitudinal direction was the film flow direction (MD) punching and condition adjustment was performed for 48 hours or more in a low temperature room controlled at 4 ° C. After condition adjustment, the temperature was controlled at 4 ° C. The sample was mounted on a tensile impact tester installed in a low temperature chamber, and the test was performed under the following conditions.
Apparatus: Tensile Impact Tester No. manufactured by Yasuda Seiki Co., Ltd. 258
Hammer capacity: 1.0J
(4) Physical property evaluation results In the physical property evaluation results, the appearance of the film is good, there is no deformation or significant fusion after high-pressure sterilization, and the physical property after sterilization is 25% of Haze, which is a measure of transparency. The physical properties of the film are as follows, provided that the tensile modulus is 200 MPa or less, which is a measure of flexibility, and the tear impact strength, which is a measure of impact resistance, is 180 KJ / m ² or more. Judgment was made as to whether the required quality was satisfied. Since the quality was satisfactory, a sheet and a medical container were prepared by the method described later, and the heat seal characteristics were evaluated. The results are shown in Table 10.

4). Production of Medical Container (1) Production of Sheet Propylene-based resin composition raw material pellets produced as described above are supplied to a single-layer or multi-layer circular die (inflation die) and are tubular at 180 to 200 ° C. After the sheet was extruded and cooled with a water-cooling ring, an inflation sheet made of a propylene-based resin composition was prepared by winding a sheet having a thickness of 0.3 mm and a folding diameter of 190 mm at a speed of 17 m / min.
(2) Preparation of medical container The above sheet is cut into a length of 300 mm, and the upper end is 20-30 mm wide from the upper end of the sheet and the lower end is 20 mm wide from the lower end of the sheet except the discharge port mounting portion, the injection port mounting portion and the drug injection portion. A container body having a peripheral portion was manufactured by heat sealing using a single-sided heating mold under the conditions of ˜30 mm, a mold temperature of 225 ° C., and a time of 4 seconds. Furthermore, the 7 mm width part of the center part of the container main body was heat-sealed using a double-sided heating mold under the conditions of a mold temperature of 120 ° C. and a time of 3 seconds to form a peelable weak seal part. Next, the weak seal portion for inhibiting communication with a width of 7 mm is heat-sealed using a double-sided heating die under the conditions of a mold temperature of 130 ° C. and a time of 5 seconds. The peelable weak seal portion for inhibiting communication was formed. And the cylindrical port member was inserted in each of the discharge port mounting part and injection | pouring port mounting part of a container main body, and it heat-sealed using the double-sided heating metal mold | die, and adhered to the container main body. In addition, a cap member equipped with a rubber elastic member was ultrasonically fused to the opening of the port member fixed to the discharge port mounting portion, and the opening was sealed.
And after filling 350 ml of 10 wt / v% amino acid aqueous solution from the opening of the port member fixed to the injection | pouring port mounting part in one chemical | medical agent chamber side divided by the weak seal part, the rubber-made elastic member is filled in the opening of the port member. The cap member equipped with was ultrasonically fused to seal the opening. After filling 150 ml of 10.7 wt / v% glucose / electrolyte aqueous solution from the drug injection part on the other drug room side, the single-sided heating mold is used for the drug injection part at a width of 10 mm, a mold temperature of 210 ° C., and a time of 3 seconds. Was used, and the medical container containing the chemical solution of the present invention shown in FIG. 1 was produced.
(3) Sterilization The medical solution-containing medical container prepared as described above is placed in a high-pressure steam sterilizer and sterilized in a nitrogen atmosphere at a temperature of 110 ° C., a gauge pressure of 1.8 kg / cm ² , and a time of 30 minutes. Cooled to room temperature.

(4) Evaluation of medical container (4-1) Evaluation of transparency After leaving a sterilized medical container containing a chemical solution for 48 hours in a nitrogen atmosphere, a part of the sheet of the container is cut out, and water at a wavelength of 450 mm is obtained. The transmittance was measured with a Shimadzu double beam self-recording spectrophotometer UV-300, and used as a measure of transparency. The results are shown in Table 11.
(4-2) Evaluation of flexibility The sterilized medical container-containing medical container sheet was cut into a dumbbell shape, and the tensile elastic modulus was measured according to JISK7113 to obtain a measure of flexibility. The results are shown in Table 11.
(4-3) Measurement of seal strength The weakly sealed portion and the peripheral portion of a medical container containing a sterilized medical solution were partially cut out, and the 180 ° peel strength was measured at a speed of 300 mm / min (the peel strength in Table 11 is It is a value converted into a width of 10 mm).
(4-4) Evaluation of heat seal characteristics (HS characteristics) In the heat seal characteristics (HS characteristics), an “attainment temperature” and a “temperature range” were calculated.
“Achieving temperature” refers to the use of the double-sided heating mold with the sealing time of the weak seal portion for communication inhibition being 5 seconds and the mold temperature from 118 ° C. to 2 when producing the medical container of (2) above. After each sample is manufactured in increments of ℃, and the prepared sample is sterilized, the strength is measured (automatically peeled off at 180 ℃) using an autograph with a width of 10 mm. ) And calculated using this graph (data), and is the ultimate temperature at a predetermined strength.
The “temperature range” was also calculated from the graph (relationship between temperature and seal strength) obtained as described above. “Temperature width” is an index of strength control ability. For example, the temperature when the strength is 4 to 8 N / 10 mm indicates how much the width is, and has a certain width. It shows that seal strength control is easy.
(4-5) Evaluation of peelability (communication) of weakly sealed portion of container Place a sterilized medical container with a medical solution on a desk and place it on the side of one storage room by hand. It was confirmed whether the part peeled (tested 5 times). The results are shown in Table 11.
(4-6) Heavy metal and eluate test A sheet cut from a medical container containing a sterilized drug solution was tested according to the Japanese Pharmacopoeia general test method "Plastic test method for infusion".
(4-7) Evaluation Results Polymer composition pellets having higher uniformity than the polymer composition of the present invention could be prepared. Moreover, the extrusion molding of the sheet | seat using the polymer composition pellet of this invention was smooth, and the foreign material, foaming, etc. were not observed. In any composition, it was confirmed that heavy metals and eluate were compatible with the Japanese Pharmacopoeia.
Table 11 shows the transparency (water permeability), flexibility (tensile modulus) and seal strength of the sheet after high-pressure steam sterilization. It turns out that the container (Example 1) using the polymer composition in this invention is excellent in transparency and a softness | flexibility.
The weak seal part peelability (communication) of the container was good, and the container could be easily communicated. The seal strength in Table 11 also supports this.

(Examples 2-9)
In the same manner as in Example 1 except that PP (A-1) to PP (A-9) obtained in Production Examples A-2 to 9 were used as the component (A), the composition, granulation, and film physical properties were evaluated. Carried out. Since the physical property evaluation results were satisfactory, the heat seal characteristics were evaluated in the same manner as in Example 1. The evaluation results for Examples 1 to 9 are shown in Table 10 and Table 12. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Comparative Examples 1-8)
Using PP (A-10) to PP (A-17) obtained in Production Examples A-10 to 17 that do not satisfy the requirements as the component (A), other than that, in the same manner as in Example 1, Granulation and film physical properties were evaluated. The evaluation results are shown in Table 13 and Table 14. The physical property evaluation results were not satisfactory. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization. In Comparative Example 7, only a film having a poor appearance was obtained due to surface roughness during molding. In Comparative Example 8, the molding was unstable and the film thickness fluctuated.

(Examples 10 to 11)
The ratio of the component (A), the component (B), and the component (C) is shown in Table 15 (the ratio of the component (A) and the component (C) is constant by changing the amount of the component (B)). Except for the above, in the same manner as in Example 1, compounding, granulation, and film property evaluation were performed. Since the physical property evaluation results were satisfactory, the heat seal characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 15. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Comparative Examples 9-11)
The ratio of the component (A), the component (B), and the component (C) is shown in Table 15 (the ratio of the component (A) and the component (C) is constant by changing the amount of the component (B)). Except for the above, in the same manner as in Example 1, compounding, granulation, and film property evaluation were performed. The evaluation results are shown in Table 15. The physical property evaluation results were not satisfactory. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Example 12)
Compounding, granulation, and film physical properties were evaluated in the same manner as in Example 1 except that PE (B-2) obtained in Production Example B-2 was used as the component (B). Since the physical property evaluation results were satisfactory, the heat seal characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 16. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Comparative Examples 12-15)
In the same manner as in Example 1 except that PE (B-3) to (B-6) obtained in Production Examples B-3 to 6 were used as the component (B), compounding, granulation, and film physical properties were evaluated. did. The evaluation results are shown in Table 16. In Comparative Examples 12 to 13, the physical properties were not satisfied, and in Comparative Example 14, streaks due to poor dispersion occurred in the film, and a film with good appearance could not be obtained. Since Comparative Example 15 satisfied the physical property evaluation results, the heat seal characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 16. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Examples 13 and 14)
The composition, granulation, and film physical properties were evaluated in the same manner as in Example 1 except that the ratio of the component (A), the component (B), and the component (C) was as shown in Table 17. Since the physical property evaluation results were satisfactory, the heat seal characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 17. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Comparative Examples 16-19)
Compounding, granulation, and film physical properties were evaluated in the same manner as in Example 1 except that the ratios of the component (A), the component (B), and the component (C) were as shown in Table 18. The evaluation results are shown in Table 18. In addition, the heat seal characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 18. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Examples 15 to 17)
In the same manner as in Example 1 except that PP (C-2) to (C-4) obtained in Production Examples C-2 to 4 were used as the component (C), compounding, granulation, and film property evaluation were performed. did. Since the physical property evaluation results were satisfactory, the heat seal characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 19. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization.

(Comparative Examples 20-25)
In the same manner as in Example 1 except that PP (C-5) to (C-10) obtained in Production Examples C-5 to 10 were used as the component (C), compounding, granulation, and film physical properties were evaluated. did. Table 20 shows the evaluation results. In Comparative Examples 20 to 22, unevenness due to poor dispersion occurred on the film surface. In Comparative Examples 23 and 25, the physical property evaluation results were not satisfied. In addition, Haze, tensile elastic modulus, and tearing impact strength in film properties are those after sterilization. Only in Comparative Example 24, the heat seal characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 20.

(Example 18)
(1) Production of Sheet Propylene-based resin composition raw material pellets of Example 1 were supplied to a single-layer circular die (inflation die), a tubular sheet was extruded at 180 to 200 ° C., and cooled with a water-cooled ring. A sheet made of a propylene-based resin composition having an average thickness of about 270 μm was prepared.
(3) Fabrication of medical container The above sheet is cut into a length of 200 mm, and the peripheral portion is cut under conditions of a width of 10 mm, a mold temperature of 225 ° C., and a time of 4 seconds except for the discharge port mounting portion and the drug injection portion. The container main body was produced by heat sealing using a single-sided heating mold. And the resin port was inserted in the discharge port mounting part of the container main body, and it heat-sealed using the double-sided heating die, and adhered to the container main body.
Then, 250 ml of 3 wt / v% amino acid injection solution was added from the drug injection part, and the drug injection part was heat-sealed using a single-sided heating mold under conditions of a width of 10 mm, a mold temperature of 225 ° C., and a time of 4 seconds. A medical container containing a chemical solution was prepared.
(4) Sterilization The medical container containing the chemical solution prepared as described above is placed in a high-pressure steam sterilizer, and high-pressure steam sterilization is performed in a nitrogen atmosphere at a temperature of 110 ° C., a gauge pressure of 1.8 kg / cm ² , and a time of 30 minutes. And cooled to room temperature.

(Example 19)
A sheet made of a propylene-based resin composition having an average thickness of about 285 μm was prepared as a sheet, and a medical container containing a chemical solution of the present invention was prepared in the same manner as in Example 18 except that it was used. Moreover, it sterilized similarly to Example 18.

(Example 20)
A sheet made of a propylene-based resin composition having an average thickness of about 300 μm was prepared as a sheet, and a medical container containing a chemical solution of the present invention was prepared in the same manner as in Example 18 except that it was used. Moreover, it sterilized similarly to Example 18.

(Comparative Example 26)
(1) 65 parts by weight of an isotactic polypropylene copolymer (flexural modulus 8200 Kg / cm ² , Vicat softening point 132 ° C., MFR 2.0), styrene ethylene butene styrene copolymer (SEBS: polystyrene content 15% by weight, MFR 1.5) , 10 parts by weight of butene content in ethylene butene copolymer), ethylene butene-1-copolymer elastomer [density 0.87 g / cm ³ , Vicat softening point 60 ° C., butene content 40% by weight, MFR (temperature 230 ° C., load 2160 g) 5.5] 25 parts by weight were added to prepare resin material pellets.
(2) Production of sheet The above raw material pellets are supplied to a single-layer circular die (inflation die), a tubular sheet is extruded at 180 to 200 ° C., cooled with a water-cooling ring, and then an average thickness of about 285 μm propylene. A sheet made of a resin composition was prepared.
(3) Fabrication of medical container The above sheet is cut into a length of 200 mm, and the peripheral portion is cut under conditions of a width of 10 mm, a mold temperature of 225 ° C., and a time of 4 seconds except for the discharge port mounting portion and the drug injection portion. The single-sided heating mold was heat sealed to produce a container body. And the resin port was inserted in the discharge port mounting part of the container main body, and it heat-sealed using the double-sided heating die, and adhered to the container main body.
Then, 250 ml of 3 wt / v% amino acid injection solution is added from the drug injection part, and the drug injection part is heat-sealed using a single-sided heating mold under the conditions of a width of 10 mm, a mold temperature of 225 ° C., and a time of 4 seconds, and a medical solution containing a drug solution A container was prepared.
(4) Sterilization The medical container containing the chemical solution prepared as described above is placed in a high-pressure steam sterilizer and sterilized in a nitrogen atmosphere at a temperature of 110 ° C., a gauge pressure of 1.8 kg / cm ² , and a time of 30 minutes. Cooled to room temperature.

(Experiment 1)
The following tests were conducted on the medical containers of Examples 18 to 20 and Comparative Example 26.
1. Pressure resistance test 50 medical containers of Examples 18 to 20 and Comparative Example 26 were held for 10 minutes at an internal pressure of 0.07 MPa for 10 minutes, and the presence or absence of leakage was confirmed. Liquid leakage was observed in all medical containers. It was not confirmed.
2. Rapid administration test Ten medical containers of Examples 18 to 20 and Comparative Example 26 (stored at 45 ° C. for 24 hours or more) were put into a pressurizer and held at an external pressure of 300 mmHg for 10 minutes to check for leakage. However, liquid leakage was not confirmed in all the medical containers of Examples 18 to 20, but liquid leakage was confirmed from one container of Comparative Example 26.
3. Drop test A drop test was performed on five medical containers of Example 18 having the thinnest sheet thickness and five medical containers of Comparative Example 26 having a thicker sheet thickness.
The drop test was carried out by dropping the bottom surface from a height of 80 cm or 100 cm cm after storing at 4 ° C. for 24 hours or more. The maximum number of drops was 10. In the 80 cm drop test, no liquid leakage was confirmed in all the medical containers of Example 18 and Comparative Example 26 after 10 drops. In the drop test of 100 cm, in the medical container of Example 18, there was one that leaked liquid at the eighth time and one that leaked liquid at the tenth time. In the medical container of Comparative Example 26, There was one that leaked liquid on the 8th time.

(Experiment 2)
The propylene-based resin composition raw material pellets of Example 1 were supplied to a single-layer circular die (inflation die), a tube-like sheet was extruded at 180 to 200 ° C., cooled with a water-cooling ring, and an average thickness of about 300 μm. A sheet made of a propylene resin composition was produced. The sheet is cut into a length of 300 mm, heat sealed with a double-sided mold and changing the mold temperature under the conditions of a width of 10 mm, a seal surface pressure of 85 N / cm ² , and a time of 5 seconds, at each mold temperature. The seal strength was measured. The result is shown in FIG.
The resin material used in Comparative Example 26 described above is supplied to a single-layer circular die (inflation die), a tubular sheet is extruded at 180 to 200 ° C., cooled with a water-cooling ring, and then propylene having an average thickness of about 300 μm. A sheet made of a resin composition was prepared. After cutting and laminating the sheet to a length of 300 mm, heat sealing is performed using a double-sided mold and changing the mold temperature under conditions of a width of 10 mm, a seal surface pressure of 85 N / cm ² , and a time of 5 seconds. The seal strength at the mold temperature was measured. The result is shown in FIG.

[Consideration by contrast between Example and Comparative Example]
Considering each of the above Examples and Comparative Examples in contrast, in the medical multi-chamber container that is composed of the novel propylene-based resin composition of the present invention that satisfies the respective regulations in the configuration of the present invention, the styrene-based Excellent flexibility, transparency and strength (drop resistance, low temperature impact resistance) without using a thermoplastic elastomer, and by controlling the heat sealing conditions, it is possible to control multi-stage stable peel strength. Obviously, it is understood that each provision of the constituent features of the present invention is reasonable and significant and confirmed by experimental data.
Specifically, the significance of each provision of component (A) is clear from Examples 1 to 9 and Comparative Examples 1 to 8, and by satisfying the requirement of the present invention for component (A), While the quality required for the chamber container is generally excellent, in Comparative Examples 1 to 8 that do not satisfy the requirements, the required quality cannot be sufficiently satisfied.
Moreover, the significance of each provision of the component (B) is clear from Examples 1 and 10 to 12 and Comparative Examples 9 to 15, and the component (B) satisfies the requirements as the component (B) of the present invention. And since a ratio is also in the prescription | regulation range of this invention and a moldability and quality are all excellent, in Comparative Examples 9-15 which do not satisfy | fill requirements, required quality cannot fully be satisfy | filled.
Furthermore, the significance of each provision of the component (C) is apparent from Examples 1 and 13 to 17 and Comparative Examples 16 to 25, and the component (C) satisfies the requirements as the component (C) of the present invention. And since a ratio is also in the prescription | regulation range of this invention and a moldability and quality are all excellent, in Comparative Examples 13-25 which do not satisfy | fill requirements, required quality cannot fully be satisfy | filled.
As described above, the propylene-based resin composition of the present invention which is excellent in various properties such as transparency, flexibility and impact resistance, is easy to control heat seal characteristics, and can be suitably used as a medical multi-chamber container. In each comparative example, the quality is generally inferior, and the superiority of the medical multi-chamber container made of the propylene-based resin composition of the present invention is highlighted.

DESCRIPTION OF SYMBOLS 1 Medical container 2 Container main body 3 Discharge port 4 Mixed injection port 5 Upper end side seal part 6 Lower end side seal part 9 Partition part 9a Central weak seal part 9b Side seal part 11 Weak seal part 21 for communication inhibition First drug chamber 22 Second drug room

Claims (10)

Propylene resin component (A) satisfying the conditions (Ai) to (A-iii) (A) to 50 to 65 wt%, ethylene-α-olefin copolymer component satisfying the conditions (Bi) to (B-iii) ( B) A propylene-based resin composition for medical containers, comprising a propylene-based resin component (C) of 10 to 20 wt% satisfying the conditions (Ci) to (C-iii) of 25 to 35 wt%.
-Conditions (Ai) to (A-iii) of the propylene resin component (A)
(Ai) Propylene-ethylene random copolymer component (A1) having a melting peak temperature of 125 to 135 ° C. and an ethylene content of 1.5 to 3.0 wt% in DSC measurement in the first step using a metallocene catalyst. ), And propylene-ethylene random block copolymer obtained by sequential polymerization of propylene-ethylene random copolymer component (A2) having an ethylene content of 8-14 wt% in the second step. Being a polymer (A-ii) Melt flow rate (JIS K7210 A method condition M, 230 ° C. 2.16 kg) is in the range of 4 to 10 g / 10 min. (A-iii) obtained by solid viscoelasticity measurement In the temperature-loss tangent (tan δ) curve, the temperature-loss tangent representing the glass transition observed in the range of −60 to 20 ° C. tan [delta) curve has a single peak, and wherein the single glass transition temperature of 0 ℃ or less, the ethylene -α- olefin copolymer component is a peak of the (B) conditions (B-i) ~ (B-iii)
(B-i) The density is in the range of 0.870 to 0.890 g / cm ³ (B-ii) The melting peak temperature is 80 ° C. or less (B-iii) Melt flow rate (JIS K7210 A method) Condition D, 190 ° C. 2.16 kg) is in the range of 2.0 to 5.0 g / 10 min. Conditions (Ci) to (C-iii) of the propylene resin component (C)
(Ci) 65-75 wt% of a polypropylene component (C1) having a melt flow rate (JIS K7210 A method, condition M, 230 ° C., 2.16 load) in the range of 100 to 200 g / 10 min in the first step, A propylene-ethylene block copolymer obtained by sequentially polymerizing 35-25 wt% of a propylene-ethylene random copolymer component (C2) having an ethylene content of 4-8 wt% and a weight average molecular weight of 800,000-3 million in two steps. (C-ii) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography, is 9.0 to 15 (C-iii) Melt flow rate of the entire propylene resin component (C) (JIS K7210 A method conditions) , 230 ° C., 2.16 load) in the range of 2.0~8.0g / 10min. Heating the container body so as to communicate with a container body having a medicine chamber formed by heat-sealing a sheet formed of the propylene-based resin composition for medical containers according to claim 1, and a lower end portion of the medicine chamber. A medical container having a sealed discharge port. The medical container has a container main body divided into a first drug chamber and a second drug chamber by a partition part from which an internal space can be peeled, a discharge port communicating with a lower end of the first drug chamber, The medical container according to claim 2, which is a multi-chamber container comprising a first medicine housed in the first medicine chamber and a second medicine housed in the second medicine chamber. The medical container according to claim 3, wherein the partition portion includes a central weak seal portion and side seal portions formed on both sides of the central weak seal portion. The medical container according to claim 4, wherein the seal strength of the central weak seal portion is lower than the seal strength of the side seal portion. The medical container according to claim 3, wherein the multi-chamber container includes a communication inhibiting weak seal portion that inhibits communication between the first drug chamber and the discharge port. The medical container according to claim 6, wherein the weak seal portion for blocking communication has a seal strength higher than that of the central weak seal portion. The medical container according to any one of claims 3 to 7, wherein a medicine is stored in each of the first medicine chamber and the second medicine chamber, and at least one medicine is a liquid medicine. 9. The medical device according to claim 8, wherein the medical container is configured such that the weak seal portion for preventing communication is peeled off simultaneously with or subsequently to the peeling of the partitioning portion by pressing the medicine chamber in which the liquid agent is stored. Container. The medical container according to any one of claims 6 to 9, wherein the partition part and the weak seal part for communication inhibition are formed by heat sealing.

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