CN111731671A - Composite material for liquid medicine packaging bag - Google Patents

Composite material for liquid medicine packaging bag Download PDF

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Publication number
CN111731671A
CN111731671A CN202010597330.9A CN202010597330A CN111731671A CN 111731671 A CN111731671 A CN 111731671A CN 202010597330 A CN202010597330 A CN 202010597330A CN 111731671 A CN111731671 A CN 111731671A
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antibacterial
layer
composite material
liquid medicine
plga
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张辉
李中明
肖瑶
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Sichuan Huili Industrial Co Ltd
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Sichuan Huili Industrial Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/40Applications of laminates for particular packaging purposes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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Abstract

The invention discloses a composite material for a liquid medicine packaging bag, which solves the problems that the antibacterial and mildewproof effects of the existing liquid medicine packaging material are uncontrollable and not lasting and need to be further improved. The composite material comprises a barrier layer, an antibacterial layer and a waterproof breathable layer from an outer layer to an inner layer in sequence, wherein the antibacterial layer comprises an antibacterial material and a viscose material, the antibacterial material is a compound of silver and PLGA, the viscose material is polyurethane, and the waterproof breathable layer is made of polyethylene. The invention has the advantages of lasting antibacterial and mildewproof effects and the like.

Description

Composite material for liquid medicine packaging bag
Technical Field
The invention relates to the technical field of liquid medicine packaging materials, in particular to a composite material for a liquid medicine packaging bag.
Background
The medicine packaging is also a crucial link as the last link of medicine production, and the quality of medicine packaging materials directly influences the quality guarantee period and even the medicine effect of the medicines.
The specific requirements of the medicine on the packaging material are as follows: high barrier property, and water vapor and oxygen are prevented from entering; ensures the quality characteristics and the components of the medicine are stable, has light weight, is convenient to carry, has low price, is convenient for clinical use, and is environment-friendly.
The existing medicine packaging materials comprise plastics, glass, metal, rubber and the like, the plastic packaging materials are commonly polyethylene, polypropylene, polyester, polyvinylidene chloride and the like, and the metal on the market at present mainly comprises aluminum materials and mainly comprises aluminum plastic bubble films, double aluminum packages and the like. However, the above packaging materials are not satisfactory for specific applications.
In order to better meet the requirements of medicine packaging materials, the adoption of high-barrier resin ethylene-vinyl alcohol copolymer, abbreviated as EVOH, which not only has high gas barrier property, but also has super oil resistance, organic solvent resistance and environmental protection property is proposed, so that the EVOH is favored for medicine packaging.
The other requirement on the medicine packaging material is that the medicine packaging material has antibacterial and mildewproof effects, the packaging material base material generally has no direct antibacterial and mildewproof effect, the common method is to sterilize the packaging bag, the packaging bottle or the packaging film, in addition, the mildewproof agent and the like are added into the medicine, and then the medicine is stored in a sealed manner, but in the medicinal process, bacterial mildews and the like can inevitably enter, so that the quality guarantee period of the medicine is short, and how to improve the antibacterial and mildewproof effects after the medicine is packaged from the packaging material is one of the problems to be solved in the field.
In the prior art, silver and/or titanium dioxide are mostly added into a base material to improve the antibacterial and mildewproof effects of the material, but the antibacterial and mildewproof effects are not controllable and lasting and need to be further improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the antibacterial and mildewproof effects of the existing liquid medicine packaging materials are uncontrollable and not lasting and need to be further improved.
The invention provides a composite material for a liquid medicine packaging bag, which solves the problems.
The invention is realized by the following technical scheme:
the composite material for the liquid medicine packaging bag sequentially comprises a barrier layer, an antibacterial layer and a waterproof breathable layer from an outer layer to an inner layer, wherein the antibacterial layer comprises an antibacterial material and a viscose material, the antibacterial material is a compound of silver and PLGA, the viscose material is polyurethane, and the waterproof breathable layer is made of PE.
The design principle of the invention is as follows: the packaging material is designed into a multilayer structure, wherein the outmost layer is a composite material with good barrier property, the middle layer is an antibacterial mildew-proof material, the inner layer is a waterproof breathable material in contact with a medicine, the waterproof breathable layer can provide a gas channel, as the moisture and air permeability of PE is good, liquid in the liquid medicine diffuses inwards through the PE waterproof breathable layer, but stays in the antibacterial layer due to the barrier of the barrier layer, water vapor gradually changes into water, PLGA gradually degrades under a water environment to release nano silver, PLGA degrades into small molecular chains and cannot stay in the antibacterial layer through the waterproof breathable layer, and the nano silver can penetrate through the PE waterproof breathable film, so that the antibacterial mildew-proof effect is realized by contact with the medicine, and the nano silver can supplement the antibacterial mildew-proof effect, and the shelf life of the medicine is prolonged.
The invention preferably selects a composite material for the liquid medicine packaging bag, and the specific form of the antibacterial material is as follows: silver is the core, PLGA is the microballon of casing, the microballon distributes in the viscose material, PLGA's casing can be with nanometer silver parcel, and in earlier stage, before PLGA did not degrade, nanometer silver can not be released, at this moment, can carry out antibiotic mould proof by the mould inhibitor of sterilizing packaging material or in the medicine itself, and the steam along with in the liquid medicine enters antibacterial layer, degrades the PLGA casing until releasing nanometer silver to play the supplementary effect to the antibiotic mould proof of medicine.
The invention preferably selects a composite material for the liquid medicine packaging bag, and the antibacterial material is prepared by adopting a microemulsion method.
Specifically, nano silver is added into a PLGA solution, the PLGA solution is emulsified into microspheres under the stirring condition of a high-pressure homogenizer, PLGA is dissolved in dichloromethane, the nano silver is dispersed into the PLGA solution under the stirring condition to form an oil phase, polyvinyl alcohol is dissolved in distilled water to form a polyvinyl alcohol aqueous phase solution, the oil phase solution is dispersed in the aqueous phase solution, high-speed stirring is adopted to obtain O/W emulsion, the organic solvent dichloromethane is removed through low-speed stirring, and the PLGA silver-coated microspheres are obtained through centrifugal collection and washing.
The invention preferably selects the composite material for the liquid medicine packaging bag, and the particle size of the microspheres is not uniform. The PLGA microspheres with different diameters have different thicknesses of the PLGA shell, so that the speeds of PLGA degradation and nano-silver release are different, and the controllable small-amount long-term release of nano-silver can be realized.
The composite material for the liquid medicine packaging bag is preferably selected, the thickness of the barrier layer is 40-50% of the total thickness of the composite material, the thickness of the antibacterial layer is 20-40% of the total thickness of the composite material, and the thickness of the waterproof breathable layer is 10-30% of the total thickness of the composite material.
The composite material for the liquid medicine packaging bag is preferably selected, the thickness of the barrier layer is 45% of the total thickness of the composite material, the thickness of the antibacterial layer is 35% of the total thickness of the composite material, and the thickness of the waterproof breathable layer is 20% of the total thickness of the composite material.
The composite material for the liquid medicine packaging bag is preferably selected, the barrier material is made of the composite material of EVOH and LDPE, the LDPE has good heat sealability, and after the LDPE is added into the EVOH, the heat sealability of the EVOH can be improved, so that the heat processing is convenient.
Further, the mass ratio of the EVOH to the LDPE is 2:1-4: 1.
Further, EVOH and LDPE are prepared using conventional coextrusion processes.
The invention has the following advantages and beneficial effects:
1. according to the invention, the medicinal packaging material is arranged into a multilayer structure, the outer layer is made of the barrier material to prevent water vapor, oxygen and the like from entering, the antibacterial layer is the nano silver wrapped by the PLGA, and the waterproof breathable layer enables the water vapor to enter the antibacterial layer, the PLGA is gradually degraded in a water environment to release the nano silver, and the nano silver can penetrate through the PE waterproof breathable film, so that the antibacterial and mildewproof effects are realized by contacting with the medicine, and the nano silver can supplement the antibacterial and mildewproof effects, so that the quality guarantee period of the medicine is prolonged.
2. The PLGA microspheres change the particle size by controlling the homogenizing pressure to obtain PLGA microspheres with different thicknesses, and under the water environment, the time for PLGA to be degraded and penetrated is different, so that the time for nano silver to be released is different, and long-acting antibiosis is realized.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a schematic structural view of the composite material of the present invention.
Reference numbers and corresponding part names in the drawings:
1-a barrier layer, 2-an antibacterial layer, 3-a waterproof breathable layer and 4-microspheres.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
The performance test items and the method of the composite material prepared by the invention are as follows:
1. gas permeability testing was performed according to standard GBT1038-2000 plastic film and sheet gas permeability test method-differential pressure method;
2. the peel strength was tested according to the standard GB/T8808-1988, Peel test methods for Soft composite plastics;
3. the heat seal strength was tested according to standard YBB00122003-2015 "Heat seal Strength test".
4. Antibacterial tests are carried out according to the standard QB/T2591-2003 'antibacterial property test method and antibacterial effect of antibacterial plastics'.
Example 1
As shown in fig. 1, the composite material for the liquid medicine packaging bag sequentially comprises a barrier layer, an antibacterial layer and a waterproof breathable layer from an outer layer to an inner layer, wherein the antibacterial layer comprises an antibacterial material and a viscose material, the antibacterial material is a compound of silver and PLGA, the viscose material is polyurethane, and the waterproof breathable layer is made of PE.
The mass ratio of the EVOH to the LDPE is 3: 1.
EVOH and LDPE are prepared by a conventional co-extrusion method.
The specific form of the antibacterial layer is as follows: and the nano silver powder and the PLGA are uniformly mixed and mixed into the viscose layer.
The preparation method comprises the following steps: dissolving PLGA in dichloromethane to form PLGA solution, adding the nano silver powder under the stirring condition, uniformly stirring, then stirring at a low speed until the dichloromethane is completely volatilized to obtain uniformly mixed nano silver powder and PLGA compound, and then pressing the compound into the polyurethane adhesive material.
The mass ratio of the silver nanopowder to the PLGA is 1:3, and the mass ratio of the PLGA to the dichloromethane is 1: 10.
The stirring speed for stirring and mixing was 1200 rpm.
The hot pressing temperature of the viscose material and the barrier layer is 160 ℃, the hot pressing pressure is 2MPa, and the hot pressing time is 10 min.
And the hot pressing temperature for pressing the compound of the nano silver powder and the PLGA into the viscose material is 20 ℃, the hot pressing pressure is 1MPa, and the hot pressing time is 5 min.
The hot pressing temperature of the waterproof breathable layer and the antibacterial layer is 150 ℃, the hot pressing pressure is 2MPa, and the hot pressing time is 10 min.
The total thickness of the composite material in the embodiment is 200-220 μm, the thickness of the barrier layer is 85-95 μm, the thickness of the antibacterial layer is 65-75 μm, and the thickness of the waterproof breathable layer is 35-45 μm.
Example 2
The difference between this embodiment and embodiment 1 is that the specific form of the antibacterial material is: silver is the core, PLGA is the microballon of casing, the microballon distributes in the viscose material, PLGA's casing can be with nanometer silver parcel, and in earlier stage, before PLGA did not degrade, nanometer silver can not be released, at this moment, can carry out antibiotic mould proof by the mould inhibitor of sterilizing packaging material or in the medicine itself, and the steam along with in the liquid medicine enters antibacterial layer, degrades the PLGA casing until releasing nanometer silver to play the supplementary effect to the antibiotic mould proof of medicine.
The antibacterial material is prepared by a micro-emulsion method.
Specifically, nano silver is added into a PLGA solution, the PLGA solution is emulsified into microspheres under the stirring condition of a high-pressure homogenizer, PLGA is dissolved in dichloromethane, the nano silver is dispersed into the PLGA solution under the stirring condition to form an oil phase, polyvinyl alcohol is dissolved in distilled water to form a polyvinyl alcohol aqueous phase solution, the oil phase solution is dispersed in the aqueous phase solution, high-speed stirring is adopted to obtain O/W emulsion, the organic solvent dichloromethane is removed through low-speed stirring, and the PLGA silver-coated microspheres are obtained through centrifugal collection and washing.
The mass ratio of the nano silver to the PLGA is 1:3, the mass ratio of the PLGA to the dichloromethane is as follows: 1:10, wherein the mass fraction of the polyvinyl alcohol aqueous phase solution is 8%, and the mass ratio of the oil phase to the aqueous phase is 1: 10.
Dividing the oil phase and the water phase into three equal parts, adding one part of the oil phase into one part of the water phase, homogenizing the first part at 8000bar of stirring speed, homogenizing the second part at 10000bar of stirring speed, homogenizing the third part at 12000bar of stirring speed, and drying to obtain microspheres with different particle sizes.
The particle size of the microspheres is not uniform. The PLGA microspheres with different diameters have different thicknesses of the PLGA shell, so that the speeds of PLGA degradation and nano-silver release are different, and the controllable small-amount long-term release of nano-silver can be realized.
Example 3 this example differs from example 1 in that the mass ratio of EVOH to LDPE was 2: 1.
example 4
The difference between the embodiment and the embodiment is that the mass ratio of the EVOH to the LDPE is 4: 1.
comparative example 1
This example differs from example 2 in that the intermediate layer does not contain an antimicrobial material, but is simply a polyurethane adhesive material.
Comparative example 2
The difference between the embodiment and the embodiment 2 is that the thickness of the PE waterproof breathable layer is 55-65 mu.
Comparative example 3
This example differs from example 2 in that the PE waterproof breathable layer has a thickness of 15-25 μ.
To verify the release rate of the antimicrobial agent, four comparative experiments were designed, each with 3 specimens, wherein the first and fourth groups were made of the composite material of comparative example 1, and the second and third groups were made of the composite material of example 2, and the antimicrobial effect of the different groups of experimental samples was measured at different time periods, specifically, the test method was: the material heat-sealing preparation of preparing this application 10ml voluminous cylinder bags, 9 total, wherein the cylinder bag of first group and second group is through the injection in the cylinder bag to the cylinder bag and decoct the traditional chinese medicine liquid that decocts, and does not add any antiseptic in the traditional chinese medicine liquid, the injection of the traditional chinese medicine liquid that adds antiseptic is adopted through the syringe to third group and fourth group, wherein the antiseptic is potassium sorbate, and the addition is 2 per mill of traditional chinese medicine liquid, and the pinhole that forms when sealing the injection with the sticky tape at last, takes out traditional chinese medicine liquid at different time quantum and carries out bacterial detection. And then counting the fungi in the traditional Chinese medicine liquid by a plate counting method, specifically, counting after 24 hours at 37 ℃ by a plate coating method, wherein the culture medium is nutrient agar. The specific experimental data and test results are shown in table 1 below:
TABLE 1 antibacterial Effect of different experimental groups
Figure BDA0002557840190000061
Figure BDA0002557840190000071
According to the growth of the bacteria, the normal traditional Chinese medicine liquid can be stored for about 2 months under the condition that the columnar bag body is sterilized and sealed, when the second month comes, as shown in the first group and the second group, the bacteria begin to appear, when the nano-silver antibacterial material is not added into the composite material for the first group, the quantity of the bacteria is increased along with the prolonging of the time, and when the second group added with the nano-silver antibacterial material enters the fourth month, the quantity of the bacteria is reduced, which proves that the antibacterial layer begins to release the nano-silver after three months, the effective sterilization effect on the traditional Chinese medicine liquid is achieved, and when the third group experiment added with the preservative in the traditional Chinese medicine liquid does not generate the bacteria from the beginning to the end, the main point is that the preservative plays a mould-proof effect firstly before the nano-silver is decomposed and released for sterilization by PLGA, and after the preservative loses a mould-proof function, the nano silver has a main sterilization effect, and the fourth group of experiments show that the nano silver can keep the traditional Chinese medicine liquid for about one year.
The detection conditions of the above examples are shown in the following table 2:
for gas permeability detection, the permeability of oxygen is mainly tested; the strains adopted in the antibacterial experiment are staphylococcus aureus and escherichia coli.
TABLE 2 Performance test results of different experimental groups
Figure BDA0002557840190000072
Figure BDA0002557840190000081
From the above test results, it can be seen that:
the blending ratio of EVOH and LDPE has a large influence on the heat seal strength and gas barrier property, when the content of EVOH is higher, the gas barrier property is better, and the heat seal strength is poorer, and when the content of LDPE is higher, the gas barrier property is reduced, and the heat seal strength is increased.
The thickness of the waterproof breathable layer is also a factor influencing the release speed of the nano-silver, when the breathable layer is thicker, the water vapor enters for a long time, and the moving path of the nano-silver is longer, so that the time for releasing the nano-silver is prolonged; on the contrary, the release time of the nano silver is short.
In the invention, the rotating speed of the low-speed stirring is 50-60 r/min.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. The composite material for the liquid medicine packaging bag is characterized in that a barrier layer, an antibacterial layer and a waterproof breathable layer are sequentially arranged from an outer layer to an inner layer, the antibacterial layer comprises an antibacterial material and a viscose material, the antibacterial material is a compound of silver and PLGA, the viscose material is polyurethane, and the waterproof breathable layer is made of PE.
2. The composite material for liquid medicine packaging bags according to claim 1, wherein the antibacterial layer is in the form of: the antibacterial material silver is used as a core, PLGA is used as microspheres of the shell, and the microspheres are distributed in the viscose material.
3. The composite material for liquid medicine packaging bags according to claim 1 or 2, wherein the antibacterial material is prepared by a microemulsion method.
4. The composite material for liquid medicine packing bags according to claim 2, wherein the microspheres have a non-uniform particle size.
5. The composite material for liquid medicine packing bags according to any one of claims 1, 2, or 4, wherein the thickness of the barrier layer is 40-50% of the total thickness of the composite material, the thickness of the antibacterial layer is 20-40% of the total thickness of the composite material, and the thickness of the waterproof breathable layer is 10-30% of the total thickness of the composite material.
6. The composite material for liquid medicine packing bags according to any one of claims 1, 2, or 4, wherein the thickness of the barrier layer is 45% of the total thickness of the composite material, the thickness of the antibacterial layer is 35% of the total thickness of the composite material, and the thickness of the waterproof breathable layer is 20% of the total thickness of the composite material.
7. The composite material for liquid medicine packing bags according to any one of claims 1, 2 or 4, wherein the barrier material is a composite of EVOH and LDPE.
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Application publication date: 20201002