JPS6351023B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to medical packaging containers. More specifically, the present invention relates to a packaging container that is substantially odorless when opened, especially when medical tools and the like are sterilized by radiation. Prior art Conventionally, disposable injection needles, disposable syringes, disposable blood collection kits, suture threads, medical nonwoven fabrics, etc. have been sterilized with a sterilizing agent such as ethylene oxide gas, and then sterilized in the same way. However, the toxicity of ethylene oxide gas to the human body cannot be ignored. Radiation sterilization has recently been proposed as a sterilization method that does not use such toxic sterilants. In the radiation sterilization method, medical tools are placed in a packaging container and then irradiated with radiation. However, radiation irradiation has negative effects such as deteriorating or discoloring packaging containers, so
Packaging container materials should be selected from those that have minimal adverse effects. Currently, packaging containers for radiation sterilization of medical devices such as those mentioned above are made of films such as polyethylene terephthalate, thermoplastic resin films such as polypropylene, polyamide, etc., and a low melting point resin film layer such as polyethylene, ethylene-vinyl acetate copolymer, etc. on the inner surface of the film. A composite film bag made of laminated layers is used. however,
When radiation sterilization is performed using such a packaging container, there is a problem in that a very small amount of decomposition products of the packaging container or medical device due to radiation irradiation remain, and this can be felt as an odor when the packaging is opened. OBJECT OF THE INVENTION Accordingly, an object of the present invention is to provide a novel medical packaging container. Another object of the present invention is to provide a packaging container that does not give off any odor after opening when sterilized by radiation. These objectives are to provide α-
A synthetic resin layer containing 50% by weight or more of an olefin-unsaturated carboxylic acid copolymer is laminated, and a filter member that communicates the internal atmosphere and the external atmosphere and is impermeable to microorganisms is attached to the bag-like material. This is achieved by medical packaging containers. The present invention also provides a packaging container in which the copolymer-containing synthetic resin layer is laminated on the entire inner surface of a bag-like object. Furthermore, the present invention provides a synthetic resin film in which the bag-like material is formed by laminating synthetic resin layers containing the copolymer,
The packaging container is formed by layering the copolymer-containing synthetic resin layer on the inner surface and heat-sealing the periphery of the copolymer-containing synthetic resin layer through the layer. Further, the present invention provides that the α-olefin-unsaturated carboxylic acid copolymer is a copolymer of ethylene and unsaturated carboxylic acid, and the unsaturated carboxylic acid is 0.5 to 20 mol%, and
This packaging container has an MFR (Melt Flow Rate) of 0.2 to 30 g/min. The present invention also provides a packaging container in which the unsaturated carboxylic acid is methacrylic acid, acrylic acid, or maleic acid. Furthermore, the present invention is a packaging container that is an ionomer resin in which 90% or less of the unsaturated carboxylic acid is neutralized with a metal compound. The present invention is a packaging container in which the metal neutralization rate of the ionomer resin is 20 to 50%. The present invention also provides a packaging container in which the copolymer-containing synthetic resin layer has a thickness of 5 to 90 μm. Furthermore, the present invention is a packaging container in which the filter member is a filtration member containing an odor adsorbent. Further, the present invention is a packaging container in which the adsorbent is activated carbon. The present invention also provides a packaging container in which the filter member is cylindrical and both ends thereof communicate with the outside and are partially fixed to the inner surface of the bag-like object. The present invention also provides a packaging container in which the filter member is a sheet-like material and is fixed to the opening of the bag-like material. The present invention also provides a packaging container in which the content of ionomer resin in the synthetic resin layers to be laminated is 80% by weight or more. The present invention also provides a packaging container in which the synthetic resin film is polyester or polypropylene. DETAILED DESCRIPTION OF THE INVENTION Next, an embodiment of the present invention will be described with reference to the drawings. That is, the medical packaging container according to the present invention, for example, the packaging container 1 for radiation sterilization, includes the first to
As shown in Fig. 3, a microorganism-impermeable cylindrical filter member 5 is attached to at least one end, usually both ends, of an airtight bag made of a synthetic resin film 2 so as to communicate with the other end. - The peripheral portion 4 is heat-sealed via the synthetic resin layer 3 containing an olefin-unsaturated carboxylic acid copolymer. α
The synthetic resin layer containing the -olefin-unsaturated carboxylic acid copolymer has the function of adsorbing decomposed products in the packaging container and suppressing the generation of decomposed products from the synthetic resin film during radiation sterilization. 4 and 5 show other embodiments of the present invention, in which one side of the inner surface of a sealed bag made of synthetic resin film 2 is coated with a synthetic resin containing an α-olefin-unsaturated carboxylic acid copolymer. It is formed by laminating layers 3, and the peripheral edge 4 is heat-sealed through the layers 3, and similarly, at least one end of the airtight bag-like article,
A microorganism-impermeable cylindrical filter member 5 is usually attached at both ends so as to communicate through the openings. 6 and 7 show still another embodiment of the present invention, in which the entire inner surface of a sealed bag made of synthetic resin film 2 contains an α-olefin-unsaturated carboxylic acid copolymer. It is formed by laminating a resin layer 3, and the peripheral edge 4 is heat-sealed through the layer 3, and is similarly impermeable to microorganisms so that at least one end, usually both ends, of the airtight bag are in communication with each other. A cylindrical filter member 5 is attached. It is more preferable to laminate the resin layer 3 on the entire inner surface of the bag-like object because generation of decomposed products from the film 2 can be suppressed over the entire surface. 8 and 9 show another embodiment of the present invention, in which a synthetic resin containing an α-olefin-unsaturated carboxylic acid copolymer is coated on the entire inner surface of a sealed bag made of a synthetic resin film 2. It is formed by laminating layers 3, and a strip-shaped microorganism-impermeable filter member 6 is attached to communicate the internal atmosphere and external atmosphere of the bag-like article, and both ends thereof are heat-sealed. The synthetic resins used in the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polypropylenes such as biaxially oriented polypropylene, and transparent thermoplastic resins such as polyamides, and have a thickness of 5 to 150 μm, preferably
It is a film of 10 to 60 μm. α-Olefin-
The unsaturated carboxylic acid copolymer-containing resin is an α-olefin-unsaturated carboxylic acid copolymer alone or a mixture of the α-olefin-unsaturated carboxylic acid copolymer and another low melting point thermoplastic resin, The content of α-olefin-unsaturated carboxylic acid copolymer is
It is 50% by weight or more, preferably 80% by weight or more. The α-olefin-unsaturated carboxylic acid copolymer is a copolymer of an α-olefin (preferably ethylene) and an unsaturated carboxylic acid (such as methacrylic acid, acrylic acid, maleic acid, etc., preferably methacrylic acid). . Further, when the unsaturated carboxylic acid is an ionomer resin having a structure neutralized with a metal, the odor removal effect is even greater. This has a structure in which long chain molecules are crosslinked with metal ions. Metals used for crosslinking include zinc, sodium, potassium, calcium,
Magnesium etc. The content of unsaturated carboxylic acid in the α-olefin-unsaturated carboxylic acid copolymer is 0.5 to 20 mol%, preferably 1 to 4 mol%. In addition, the neutralization rate by the metal is 90% or less,
Preferably it is 20-50%. Additionally, MFR
(ATSM D1238) is 0.2-30g/min, preferably
It is 0.7-15 g/min. The amount of unsaturated carboxylic acid is preferably in the above range because when it is 0.5 mol % or more, the odor removal effect after radiation irradiation is excellent, while when it is 20 mol % or less, it is excellent in terms of physical properties such as flow characteristics of the resin. Further, regarding the neutralization rate by metal, when it is 20% or more, the odor removal effect after radiation irradiation is excellent, whereas when it exceeds 90%, the physical properties such as flow characteristics of the resin deteriorate. In addition, as the low melting point thermoplastic resin blended into this α-olefin-unsaturated carboxylic acid copolymer, there are transparent resins such as polyethylene and ethylene-vinyl acetate copolymer, and their number average molecular weight is
50,000 to 1,000,000, preferably 100,000 to 500,000. Such an α-olefin-unsaturated carboxylic acid copolymer-containing resin layer can be formed by, for example, extruding a molten α-olefin-unsaturated carboxylic acid copolymer-containing resin onto the surface of a synthetic resin layer through a die and press-bonding it. , laminated by a method such as extruding both resins simultaneously from separate dies and pressing them immediately, and the thickness after lamination is 30 to 150 μm, preferably 40 to 90 μm.
It is. The laminated sheet thus formed is folded with the α-olefin-unsaturated carboxylic acid copolymer-containing resin layer inside, or two sheets are stacked with the resin layers inside each other, and A tool is placed between them, and a microorganism-impermeable cylindrical filter member is heated at the peripheral edge of the overlapping portion of the laminated film so that both ends thereof reach both ends of the laminated sheet and both ends are not blocked. The container is sealed by sealing and then sterilized by irradiation with radiation, thereby obtaining the packaging container shown in FIGS. 1 to 7. Further, the laminated sheets are connected at both ends thereof through a band-shaped microorganism-impermeable filter member, and then both ends of a cylindrical body having an α-olefin-unsaturated carboxylic acid copolymer-containing resin layer inside are connected. The filter is sealed by heat sealing using high frequency or other methods, and the internal atmosphere and external atmosphere are communicated through the filter section. In addition to filter paper, filter members used in the present invention include synthetic fibers such as polyester, polyethylene, and polyamide, or nonwoven fabrics of activated carbon fibers, etc., in the shape of a tube, band, or other shapes.
Further, a layer of an adsorbent such as activated carbon fiber, activated clay, activated alumina, or zeolite is provided on any side of these members, preferably on the inner space side of the bag-like object, or
Alternatively, even better results can be obtained by mixing these adsorbents with the filter paper, nonwoven fabric, etc. The radiation used includes electromagnetic radiation such as gamma rays and electron beams, preferably gamma rays. The irradiation intensity is 1-5 Mrad, preferably 2
~3 Mrad. Therefore, medical devices to be subjected to radiation sterilization using the packaging container according to the present invention include, for example, disposable syringe needles, disposable syringes,
These products include disposable blood collection kits, sutures, medical non-woven fabrics, absorbent cotton, artificial blood vessels, catheters, etc. Next, the present invention will be explained in more detail by giving Examples. Example 1 An ethylene-methacrylic acid copolymer with a methacrylic acid content of 3.0 mol% is neutralized to 30% with zinc.
A resin composition consisting of 90 parts by weight of an ionomer resin for MFR 5.0 g/min and 10% by weight of polyethylene (number average molecular weight 100000) was laminated to a thickness of 20 μm on the entire surface of a 16 μm thick polyethylene terephthalate film to obtain a laminated film. Ta. This laminated film
Fold the ionomer resin composition layer side inward, insert a disposable syringe between them,
Next, a cylindrical paper filter member was held between the folded edges of the laminated film so that both ends of the filter member reached both ends of the laminated film, and then the peripheral edges were heat-sealed. Next, 2.5 Mrad gamma rays were irradiated, and two weeks later, an odor sensory test was conducted by 20 sensory examiners in the following manner. That is,
Immediately after opening the package, bring your nose close to it and smell it. The results are shown in Table 1 "Grades of odor intensity according to Yaglou" (Hygiene Test Methods/Annotations 1980, P1046)
Evaluation was made according to the following. One sample envelope was opened every 5 minutes. The order in which the samples were given to the 20 people was not fixed. The results are shown in Table 2. Example 2 In the method of Example 1, the methacrylic acid content
From 90 parts by weight of an ionomer resin with an MFR of 14.0 g/min made by neutralizing 3.0 mol% ethylene-methacrylic acid copolymer with 25% zinc and 5 parts by weight of ethylene-vinyl acetate copolymer (number average molecular weight 70,000). A packaging container was manufactured in the same manner except that a resin composition of 1 was used as the inner layer, and the same tests were conducted, and the results shown in Table 2 were obtained. Example 3 A packaging container was manufactured in the same manner as in Example 1, except that biaxially oriented polypropylene was used instead of polyethylene terephthalate as the outer layer, and the same tests were conducted, as shown in Table 2. The results were obtained. Example 4 In the method of Example 1, biaxially oriented polypropylene was used instead of polyethylene terephthalate as the outer layer, and ethylene-acrylic acid copolymer (MFR 9 g/min. manufactured by Mitsubishi Yuka Co., Ltd.) resin was used as the inner layer. A packaging container was manufactured in the same manner except for the above, and the same tests were conducted, and the results shown in Table 2 were obtained. Similar results were also obtained when ethylene-methacrylic acid copolymer resin and ethylene-maleic acid copolymer resin were used as the inner layer. Example 5 A packaging container was manufactured in the same manner as in Example 1, except that a cylindrical body made of activated carbon fiber was used as the filter member, and the same tests were conducted. The results shown in Table 2 were obtained. was gotten. Comparative Example 1 The method of Example 1 except that polyethylene (number average molecular weight 90,000) was used as the inner layer,
When packaging containers were manufactured in a similar manner and subjected to similar tests, the results shown in Table 2 were obtained. Comparative Example 2 A packaging container was manufactured in the same manner as in Example 1, except that an ethylene-vinyl acetate copolymer (number average molecular weight 70,000) was used as the inner layer, and the same tests were conducted. The results shown in Table 2 were obtained. Comparative Example 3 The method of Example 1 except that polyethylene (number average molecular weight 90,000) was used as the inner layer,
When packaging containers were manufactured in a similar manner and subjected to similar tests, the results shown in Table 2 were obtained. Comparative Example 4 A packaging container was manufactured in the same manner as in Example 1, except that an ethylene-vinyl acetate copolymer (number average molecular weight 70,000) was used as the inner layer, and the same tests were conducted. The results shown in Table 2 were obtained. Table 1 Degree of odor intensity 0 Odorless 1/2 Minimal (very slightly felt) 1 Clear (not felt or unpleasant) 2 Average - 3 Strong (unpleasant) 4 Very strong (very unpleasant) 5 Unbearable (nausea)

[Table] Specific Effects of the Invention As described above, the medical packaging container according to the present invention has an α-olefin-unsaturated carboxylic acid copolymer on at least a portion of the inner surface of the airtight bag made of a synthetic resin film. Because it is made of laminated synthetic resin layers containing 50% by weight or more of a polymer, and is equipped with a filter member that communicates the internal atmosphere with the external atmosphere and is impermeable to microorganisms, it cannot be irradiated with radiation. When sterilization is carried out, not only is there little deterioration due to radiation, but the generated odor is also substantially adsorbed to the resin layer containing the α-olefin-unsaturated carboxylic acid copolymer, and some of it is absorbed by the filter member. After that, they escape to the outside. In this case, if the filter member is band-shaped, it directly enters the external atmosphere, or if it is cylindrical, it enters the cylindrical filter member from a bag-like object and then flows through the cylindrical body to its open end. escapes from the body into the external atmosphere. Therefore, even better results can be obtained if the filter member is given adsorption ability. In addition, since the copolymer-containing resin layer is laminated on the entire inner surface of the bag-like product, the packaging container can more completely suppress the generation of decomposed products from the synthetic resin film, and has a larger area. Adsorption effect increases. Furthermore, when the α-olefin is ethylene, it is more preferable because it is difficult to be decomposed by gamma rays, and when the unsaturated carboxylic acid is 0.5 mol% or more, it has excellent adsorption properties, and when it is 20 mol% or less, it has excellent processability and MFR is low. When it is in the range of 0.2 to 30 g/min, the processability is excellent. Furthermore, when the unsaturated carboxylic acid is methacrylic acid, acrylic acid, or maleic acid, the adsorption properties are particularly excellent. Further, if the content of the α-olefin-unsaturated carboxylic acid copolymer is 80% by weight or more, the adsorption properties will be even better. Furthermore, by using polyester or polypropylene as the synthetic resin film, heat resistance can be increased during heat sealing. Further, when the unsaturated carboxylic acid is an ionomer resin having a structure neutralized with a metal, the odor removal effect is even greater. In addition, the metal neutralization rate of ionomer resin is
If it is 20% or more, it has excellent odor adsorption properties, while if it is 50% or less, it is difficult to decompose. Furthermore, it is preferable that the copolymer-containing synthetic resin has a thickness of 5 to 90 μm in terms of hardness as a packaging container and prevention of pinholes during manufacturing. Furthermore, by making the filter member cylindrical, continuous production is facilitated, and since the filter member communicates the inside of the packaging container with the outside atmosphere, decomposition products generated inside the packaging container will be removed during storage. Diffusion to the outside is more preferable in terms of odor removal. Furthermore, since the internal air can be exhausted, there is an advantage that it does not take up much space during storage or transportation.

[Brief explanation of the drawing]

FIG. 1 is a perspective view showing an example of a packaging container according to the present invention, FIG. 2 is a sectional view taken along the line - in FIG. 1,
3 is a sectional view taken along the - line in FIG. 1, FIG. 4 is a sectional view similar to FIG. 2 showing another embodiment, and FIG.
The figure is a sectional view similar to FIG. 3 showing another embodiment, FIG. 6 is a sectional view similar to FIG. 2 showing another embodiment, and FIG. 7 is a sectional view similar to FIG. 8 is a perspective view showing another embodiment, and FIG. 9 is a sectional view taken along the line - in FIG. 8. 1...Packaging container, 2...Synthetic resin layer, 3...α
- Olefin-unsaturated carboxylic acid copolymer-containing resin layer, 4... peripheral portion, 5, 6... filter member.

Claims (1)

[Scope of Claims] 1. A synthetic resin layer containing 50% by weight or more of an α-olefin-unsaturated carboxylic acid copolymer is laminated on at least a portion of the inner surface of a sealed bag made of a synthetic resin film, A medical packaging container comprising a filter member which communicates the internal atmosphere with the external atmosphere and is impermeable to microorganisms and is attached to the bag-like object. 2. The packaging container according to claim 1, wherein the copolymer-containing synthetic resin layer is laminated over the entire inner surface of the bag-like article. 3. The bag-like object is made by laminating synthetic resin films containing the copolymer-containing synthetic resin layers so that the copolymer-containing synthetic resin layer is located on the inner surface, and then applying the synthetic resin film at the periphery via the layer. The packaging container according to claim 2, which is heat-sealed. 4 The α-olefin-unsaturated carboxylic acid copolymer is an ethylene-unsaturated carboxylic acid copolymer, and the unsaturated carboxylic acid is 0.5 to 20 mol% and
Claim 1 in which the MFR is 0.2 to 30 g/min
The packaging container described in any one of Items 1 to 3. 5. The packaging container according to claim 4, wherein the unsaturated carboxylic acid is methacrylic acid, acrylic acid, or maleic acid. 6. The packaging container according to claim 4, which is an ionomer resin in which 90% or less of the unsaturated carboxylic acid is neutralized with a metal compound. 7. The metal neutralization rate of the ionomer resin is 20 to 50%.
The packaging container according to claim 4. 8 The thickness of the copolymer-containing synthetic resin layer is 5 to 90μ
The packaging container according to any one of claims 1 to 7, which is m. 9. The packaging container according to claims 1 to 8, wherein the filter member is a filtration member containing an odor adsorbent. 10 Claim 9 in which the adsorbent is activated carbon
Packaging containers listed in section. 11. The packaging container according to claims 1 to 10, wherein the filter member is cylindrical, and both ends thereof communicate with the outside and are partially fixed to the inner surface of the bag-like object. 12. The packaging container according to claims 1 to 10, wherein the filter member is a sheet-like material and is fixed to the opening of the bag-like material. 13 The content of α-olefin-unsaturated carboxylic acid copolymer in the synthetic resin layer to be laminated is 80% by weight
A packaging container according to any one of claims 1 to 12 as described above. 14. The packaging container according to any one of claims 1 to 13, wherein the synthetic resin film is polyester or polypropylene.