JPH0985913A - Plastics film for liquid container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid container film for medicine wherein its transpar ency is excellent and eluate into content liquid is little by a method wherein a polypropylene film in which isotactic polypropylene and/or an olefin elastomer are mixed is laminated on at least one side surface of a transparent base mate rial film. SOLUTION: A polypropylene film layer 1 is obtained by making a film from that which isotactic polypropylene wherein ethylene as a polymeric modifier is copolymerized with syndiotactic polypropylene and/or an olefin elastomer is mixed in. The polypropylene film layer 1 is laminated on one side surface of a base material layer 2 of a transparent film to form a plastic film for a liquid container A. Therefore, it is excellent in transparency, its eluate into content liquid is little, it combines thermal adhesion with heat resistance to pasteurization at a high temperature, and flexibility, impact resistance, etc., at a low temperature, and it can be used as a forming material of the liquid container for medicine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic film for a liquid container which is particularly preferably used as a material for forming a medical liquid container such as an infusion solution, a drug solution or a blood bag.

[0002]

2. Description of the Related Art Infusion solution,
Medical liquid containers such as drug solutions and blood bags need not only have high strength and excellent safety, but it is also required that the content liquid can be visually checked from outside the container. The characteristic of high transparency is a great advantage in the medical liquid container. Conventionally, as such a medical liquid container, a glass bottle, a blow molding bottle such as polyethylene or polypropylene, a bag made of polyethylene or polyvinyl chloride, or a container using an ethylene-vinyl acetate copolymer film as a forming material is used. However, these medical liquid containers have various problems as described below.

That is, since glass bottles are easily broken, it is necessary to handle them carefully, and since air inlets are required at the time of use, foreign substances and germs may be mixed in, so consideration should be given to them. In addition to the above, depending on the method of use of the glass bottle, the alkaline substance contained in the glass may be eluted into the content liquid, so the method of use is limited, and there is a problem that it is hard to dispose because it is hard. is there. Blow-molded bottles, polyethylene or polyvinyl chloride bags, and ethylene-vinyl acetate copolymer containers lack transparency and poor resistance to high-temperature sterilization such as retort sterilization, and further plasticizers and antioxidants. ,
Since it contains low molecular weight components such as a stabilizer and residual vinyl chloride monomer, these components are liable to elute into the content liquid depending on the method of use of the container, which poses a sanitary problem, thus limiting the method of use. Further, in the case of ethylene-vinyl acetate copolymer, there is a problem that it must be cross-linked with an electron beam or the like to improve its heat resistance.
Environmental problems such as normal disposal cannot be performed because harmful gas is generated by combustion.

The present invention has been made in view of the above circumstances, is excellent in transparency, and has little eluate in the content liquid,
Furthermore, it also has other properties required for a medical liquid container, such as heat adhesiveness, heat resistance against high temperature sterilization such as retort sterilization (eg, 121 ° C. treatment), flexibility at low temperature, and impact resistance. An object of the present invention is to provide a plastic film for a liquid container, which is useful as a material for forming a liquid container for liquid.

[0005]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present invention has at least one surface of a transparent substrate film, on which syndiotactic polypropylene and isotactic polypropylene obtained by copolymerizing ethylene and / or Provided is a plastic film for a liquid container, which is obtained by laminating a polypropylene film formed by blending an olefin elastomer. Here, as the substrate film, one or two selected from the group consisting of polyamide, polyethylene terephthalate, polypropylene and ethylene-polyvinyl alcohol copolymer film.
It is more preferable to use a film made of one or more kinds of films.

The plastic film for a liquid container of the present invention comprises, as its film-forming material, a transparent substrate film and isotactic polypropylene obtained by copolymerizing syndiotactic polypropylene with ethylene as a polymeric modifier and / or A polypropylene-based film blended with an olefin-based elastomer, which is a multilayer structure film obtained by laminating these by means such as extrusion lamination, dry lamination, or coextrusion film forming processing. It is intended to obtain a plastic film having not only excellent properties but also having heat resistance, flexibility and impact resistance. The above-mentioned polymer-based modifier is compounded mainly for the purpose of improving low temperature impact resistance.

Here, as the film material of the base film, a group consisting of polyamide, polyethylene terephthalate, polypropylene and ethylene-polyvinyl alcohol copolymer films, which are plastic films having excellent transparency and relatively high mechanical strength. By using one or more kinds of films selected from the above, it is possible to obtain a superior plastic film for liquid containers, which is easy to prepare a film and has the film characteristics of these plastics.

As the olefin elastomer,
Ethylene-based elastomers and / or propylene-based elastomers, especially ethylene or propylene and α-, respectively.
Use of an elastomer obtained by copolymerizing with an olefin further improves film characteristics such as low temperature impact resistance and transparency of the polypropylene film.

When the polypropylene-based film uses ethylene-copolymerized isotactic polypropylene or olefin-based elastomer as the polymer-based modifier, syndiotactic polypropylene 60-
For 95% by weight, 5% of isotactic polypropylene or olefin elastomer copolymerized with ethylene is used.
On the other hand, in the case of using isotactic polypropylene copolymerized with ethylene and an olefin elastomer as a high molecular weight modifier, syndiotactic polypropylene is added to ethylene in an amount of 40 to 90% by weight. Polymerized isotactic polypropylene 5
It is more effective to add -30% by weight and 5-30% by weight of an olefin elastomer.

The plastic film for a liquid container of the present invention can make more effective use of the characteristics of the polypropylene film in the multilayer structure film, if the polypropylene film is used as the innermost layer of the liquid container. it can.

When the film thickness of the polypropylene film is 20 to 200 μm, a plastic film for liquid containers can be obtained in which the film characteristics of the polypropylene film are exhibited more suitably.

The plastic film for a liquid container of the present invention has excellent film properties such as excellent transparency, almost no elution of organic substances, and high film strength. It is particularly useful as a material for forming a medical liquid container, which is required not only to have little elution of organic substances but also to be excellent in transparency.

[0013]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a longitudinal sectional view of a plastic film A for liquid containers of the present invention. The plastic film A is a multi-layered film including a polypropylene film layer 1 and a base material layer (base material film) 2.

The polypropylene type film layer 1 is formed by mixing syndiotactic polypropylene with isotactic polypropylene obtained by copolymerizing ethylene as a polymer type modifier and / or an olefin type elastomer. The layer thickness (film thickness) is not particularly limited, but is preferably 20 to 200.
It is preferable that the thickness is μm, more preferably 50 to 100 μm. If it is less than 20 μm, for example, when it is used as a material for forming a liquid container for medical use, the necessary mechanical strength may not be obtained, and if it exceeds 200 μm, the film thickness of the plastic film A becomes too thick, resulting in transparency. It may be slightly chipped.

The polypropylene film layer 1 does not have to be a single-layer film having a single constitution. For example, a film obtained by blending syndiotactic polypropylene with an olefin elastomer is composed of A and the same components as A. A'is a film having a different blending ratio, B is a film obtained by blending isotactic polypropylene obtained by copolymerizing syndiotactic polypropylene with ethylene, and B'is a film having the same components as B and having a different blending ratio thereof. When a film obtained by mixing isotactic polypropylene obtained by copolymerizing ethylene with syndiotactic polypropylene and an olefin-based elastomer is composed of C, C and the same components, and a film having a different mixing ratio thereof is C ′, Depending on its purpose and use, for example, A / B / A, A / / A, A / B, A / C, A / A
‘/ A, B / B’ / B, C / C ’/ C, etc.
It is also possible to properly combine the respective films of C ′ to obtain a multilayer film in which multiple layers are laminated.

The material and layer thickness of the base material layer 2 are not particularly limited as long as they are transparent films, but stretched or biaxially stretched polyamide film, polyethylene phthalate, polypropylene, ethylene-polyvinyl alcohol It is preferable that the film is excellent in transparency obtained from the polymer and is formed of a film having relatively large strength, and the layer thickness thereof is preferably 10 to 50 μm,
More preferably, it is 12 to 30 μm. If it is less than 10 μm, for example, when it is used as a material for forming a liquid container for medical use, necessary strength may not be obtained, and if it exceeds 50 μm, flexibility and transparency desirable as a material for forming a liquid container for medical use may be obtained. You may not be able to. The base material layer 2 may be formed by appropriately combining and laminating the above plastic films.

The plastic film A having the above structure can be manufactured as follows.

First, the syndiotactic polypropylene used is not particularly limited in its physical properties, but the syndiotactic pentad fraction measured by ¹³ C-NMR is 0.7 or more, particularly 0.77. Is about 0.99, and the melt flow index measured at 230 ° C. is 0.01 to 100 g / 10 minutes, particularly 0.1 to 20.
It is preferably about g / 10 minutes. Outside the above range, the desired physical properties may not be obtained in some cases. The density is preferably 0.88 to 0.9, and sufficient transparency may not be obtained outside the above range.

The olefin elastomer used as the polymer modifier is preferably an ethylene elastomer or a propylene elastomer, more preferably an elastomer obtained by copolymerizing ethylene or propylene with an α-olefin. In this case, if the α-olefin is blended in a proportion of 15 to 30% by weight with respect to 70 to 85% by weight of ethylene or propylene, the transparency of the polypropylene film will be further improved. Also,
Examples of the α-olefin include 1-butene, 1-hexene, propylene and the like, and among these, 1-butene or 1-hexene is preferably used.
In the olefin elastomer of the present invention, an ethylene elastomer and a propylene elastomer can be used alone or in combination. The olefin elastomer of the present invention is 19
Melt flow index measured at 0 ° C is 0.1-5
The amount is preferably 0 g / 10 minutes, particularly preferably about 1 to 20 g / 10 minutes, and outside the range, the desired physical properties may not be obtained in some cases.

As the isotactic polypropylene copolymerized with ethylene used as a polymer modifier, a random copolymer or a block copolymer containing 1 to 6% by weight of ethylene is suitable. If the amount of ethylene is less than 1% by weight, the effect of forming a copolymer with ethylene may not be sufficiently obtained. If the amount of ethylene exceeds 6% by weight, the polypropylene film obtained has a low melting point, resulting in poor usability. May be. As the random copolymer, one having a melt flow index measured at 190 ° C. of 0.1 to 50 g / 10 minutes, particularly about 1 to 20 g / 10 minutes is preferably used.

In the plastic film A for liquid containers of the present invention, when either one of isotactic polypropylene copolymerized with ethylene or an olefin elastomer is blended as a polymer type modifier, syndiotactic polypropylene is added in an amount of 60 to 60%. 95% by weight, especially 70-80
% By weight, 5-40% by weight of polymeric modifier, especially 20-
Preferably, it is 30% by weight. Outside the above range,
In some cases, it may be difficult to obtain the desired film characteristics of the present invention. Further, when both the isotactic polypropylene copolymerized with ethylene and the olefin elastomer are blended as the polymer-based modifier, the syndiotactic polypropylene is blended for the same reason as above.
0 to 90% by weight, particularly 60 to 80% by weight, and 5 to 30% by weight, especially 10 to 2 of ethylene-copolymerized isotactic polypropylene and olefin elastomer, respectively.
It is preferably 0% by weight.

When the polypropylene-based film layer 1 and the base material layer 2 are each a single-layer film having a single structure, the film material blended in the above ratio is coextruded together with, for example, polyamide which is the film material of the base material layer 2. By processing the film, the polypropylene-based film layer 1 and the base material layer 2 are integrally formed into a film. The method for forming the plastic film A is not limited to the coextrusion film forming process. For example, the polypropylene film layer 1 and the base material layer 2 are formed as single layer films in advance, and the purpose of the present invention is to A method of laminating these by using an appropriate adhesive resin or anchoring agent that does not interfere, extruding the base material layer 2 as a monolayer film in advance, and melting and adhering the polypropylene film layer 1 thereon. A laminating method or the like can also be adopted. Also, the polypropylene film layer 1
Also when each of the base material layer 2 and the base material layer 2 is a multi-layer film, it can be produced in the same manner as described above, and the polypropylene-based film layer 1 and the base material layer 2 are formed in advance, respectively, and then these are formed. The plastic film A for liquid containers may be manufactured by laminating, or the plastic film A for liquid containers may be manufactured by integrally forming the polypropylene film layer 1 and the base material layer 2.

The plastic film A for liquid containers of the present invention comprises a polypropylene film layer 1 and a base material layer 2.
The present invention is not limited to the two-layer structure composed of and, and as shown in FIG. 2, polypropylene-based film layers 1 and 1 may be laminated on both surfaces of the base material layer 2, respectively. In this case, the polypropylene-based film layers 1 and 1 may be made of polypropylene-based films having the same structure, or may be made of polypropylene-based films having different structures.

The polypropylene film thus obtained preferably has a transparency measured by JIS-K-7105 of 80% or more, and more preferably 90% or more.

The plastic film A for a liquid container can be used as a material for forming an infusion bag, for example. In this case, for example, plastic film A
Polypropylene film layer 1
After stacking so that it becomes the innermost layer of the container, an injection part with a cap for the content liquid (infusion in this case) is provided, and a flat rectangular bag with four circumferences sealed except that the injection part is open A bag is created by means such as impulse seal, fusing seal or hot plate seal so that it becomes a shape or a standing shape, and the infusion solution is hermetically stored in the bag by means such as injecting the infusion solution from the injection part and tightening the cap. Then, it can be used for storage and transportation of the infusion solution by subjecting it to heat sterilization by heating at 105 to 125 ° C. for 0.5 to 2 hours.

[0027]

EXAMPLES The present invention will be described below based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 4 and Comparative Examples 1 to 3] The polypropylene films of Examples 1 to 4 and Comparative Examples 1 to 3 having the structure shown in Table 1 so that the thickness was 100 μm by the T die casting method. Was formed into a film, and the transparency of each polypropylene film was measured according to JIS-K-7105.
The results are also shown in Table 1. In addition, each film was laminated on both sides of a biaxially stretched polyamide film having a thickness of 15 μm using a urethane adhesive to prepare a plastic film for a liquid container having a total thickness of about 220 μm, and a bag made of each film. Was subjected to the following drop impact strength test.
The results are also shown in Table 1. The syndiotactic polypropylene is SPH-0401 [trade name: manufactured by Mitsui Toatsu Chemicals, Inc .: intrinsic viscosity measured with a tetralin solution at 135 ° C. is 1.28 dl / g, 1,2,4-tris at 125 ° C.]. The syndiotactic pentad fraction measured by ¹³ C-NMR at 67.5 MHz in a chlorobenzene solution was 0.79.
Ratio of weight average molecular weight and number average molecular weight measured with 1,2,4-trichlorobenzene solution at 3,135 ° C (Mw / M
n) is 2.4, the melt flow index measured at 230 ° C. is 4.4 g / 10 min], and the polymer-based modifier is Tufmer XR-110T [trade name: Mitsui Petrochemical Industry Co., Ltd.] which is a propylene-based elastomer. )], Tufmer A-4085 [trade name: manufactured by Mitsui Petrochemical Industry Co., Ltd.], which is an ethylene-based elastomer, and isotactic polypyrropylene copolymerized with ethylene is Mitsui Noblene EFL560.
[Brand name: manufactured by Mitsui Toatsu Chemicals, Inc.] and the biaxially stretched polyamide film used was Emblem [Brand name: manufactured by Unitika Ltd.] which is a biaxially stretched nylon 6 film.

JIS-K-7105: Total light transmittance (transmissivity
Lightness) The test plastic film is cut into 50 × 50 mm to obtain a test piece. 3 pieces for each plastic film
Prepare one by one. N, which is an integrating sphere type light transmittance measuring device
A test piece is attached to DH-Σ80 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the total amount of transmitted light (transparency) is measured. Drop impact strength test Using a plastic film, heat sealing conditions were 180 to 210 ° C., 2 kg / cm ² , 1 to 2 seconds,
Purified water 500 ml in a 150 x 200 mm three-sided sealed bag
After being filled with, was subjected to a heat sterilization treatment for 60 seconds under a temperature condition of 121 ° C., and then freely dropped from a height of 1.2 m. For each example and comparative example, five three-sided sealed bags were produced (n = 5), each bag was continuously dropped seven times, and the results were averaged.

[0030]

[Table 1]

According to the results shown in Table 1, the polypropylene film of the present invention is excellent not only in transparency but also in low-temperature impact resistance as a plastic film for liquid containers, and particularly in the formation of liquid containers for medical use. It is recognized that it is useful as a material. On the other hand, in the case of a polypropylene-based film consisting only of syndiotactic polypropylene (Comparative Example 1), the transparency was excellent, but the low-temperature impact resistance as a plastic film for liquid containers was poor, while the ethylene-copolymerized polypropylene was used. In the case of a polypropylene film made of only a block copolymer (Comparative Example 2) or a polypropylene film made of an ethylene elastomer and an ethylene random copolymerized isotactic polypropylene (Comparative Example 3), the transparency is poor,
It is recognized that not only is it unsuitable as a material for forming a liquid container for medical use which requires that the content liquid can be visually observed from the outside, but it is also inferior in low temperature impact resistance as a plastic film for a liquid container.

[0032]

EFFECTS OF THE INVENTION According to the present invention, the transparency is excellent, the amount of elution in the content liquid is small, and other characteristics required for a medical liquid container, such as heat adhesiveness, retort sterilization, etc. It is possible to obtain a plastic film for a liquid container which has heat resistance against high temperature sterilization, flexibility at low temperature, impact resistance, etc. and is particularly useful as a material for forming a liquid container for medical use.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view showing one mode of a plastic film for a liquid container of the present invention.

FIG. 2 is a longitudinal sectional view showing another embodiment of the plastic film for liquid containers of the present invention.

[Explanation of symbols]

 A Plastic film for liquid container 1 Polypropylene film layer 2 Base material layer (base material film)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/34 B32B 27/36 27/36 A61J 1/00 331C

Claims (8)

[Claims] 1. A polypropylene-based film prepared by blending syndiotactic polypropylene with isotactic polypropylene and / or olefin-based elastomer obtained by copolymerizing ethylene with at least one surface of a transparent substrate film. A plastic film for a liquid container, which is characterized in that 2. The plastic film for a liquid container according to claim 1, wherein the base film comprises one or more films selected from the group consisting of polyamide, polyethylene terephthalate, polypropylene and ethylene-polyvinyl alcohol copolymer films. . 3. The plastic film for a liquid container according to claim 1, wherein the olefin-based elastomer is an ethylene-based elastomer and / or a propylene-based elastomer. 4. The polypropylene film contains 60 to 95% by weight of syndiotactic polypropylene and 5 to 40% by weight of isotactic polypropylene copolymerized with ethylene or an olefin elastomer. A plastic film for a liquid container as described above. 5. The polypropylene film comprises 40 to 90% by weight of syndiotactic polypropylene and 5 to 3 of isotactic polypropylene copolymerized with ethylene.
The plastic film for a liquid container according to claim 1, 2 or 3, comprising 0% by weight and 5 to 30% by weight of an olefin elastomer. 6. An ethylene-based elastomer or a propylene-based elastomer, which is obtained by copolymerizing ethylene or propylene with an α-olefin, respectively.
A plastic film for a liquid container as described above. 7. The plastic film for a liquid container according to claim 1, wherein the polypropylene film forms the innermost layer of the liquid container. 8. The plastic film for a liquid container according to claim 1, wherein the polypropylene film has a film thickness of 20 to 200 μm.