CN111761898B - Medical packaging film and preparation method thereof - Google Patents
Medical packaging film and preparation method thereof Download PDFInfo
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- CN111761898B CN111761898B CN202010636850.6A CN202010636850A CN111761898B CN 111761898 B CN111761898 B CN 111761898B CN 202010636850 A CN202010636850 A CN 202010636850A CN 111761898 B CN111761898 B CN 111761898B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention is suitable for the technical field of materials, and provides a medical packaging film and a preparation method thereof, wherein the medical packaging film comprises an outer film layer, an inner film layer and a phase change energy storage material packaged between the outer film layer and the inner film layer; the adventitia layer includes: 65-80 parts of polylactide, 3-9 parts of polybutylene succinate, 4-8 parts of nanocellulose and 3-8 parts of ethylene isophthalate; the intima layer includes: 65-80 parts of polylactic acid-glycollic acid copolymer, 8-12 parts of zinc chloride solution, 4-8 parts of nano cellulose, 4-8 parts of calcium propionate and 0.5-5 parts of polyethylene glycol terephthalate; the phase-change energy storage material is prepared from a sodium chloride solution, a starch water-absorbing resin, sodium polyacrylate and phase-change paraffin according to the weight ratio of 1: (3-5): (2-4): (0.01-0.03) by mixing. The film layers of the invention have wide raw material sources, are green and environment-friendly, have degradability, excellent barrier property, mechanical property and high transparency, can protect medical articles, and simultaneously, the phase change energy storage material has good and durable cold storage effect and high recycling rate.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a medical packaging film and a preparation method thereof.
Background
In order to prevent medical drugs and medical devices from being affected by external environments such as environmental temperature, bacteria, dust and the like in various processes of production, storage, transportation and the like, the medical drugs and the medical devices are often required to be placed in a packaging film and be always required to be in a specified low-temperature environment so as to prevent the medical drugs and the medical devices from being infected and lost and ensure the quality of the medical drugs and the medical devices. Among them, the transportation process of medical drugs and medical devices is often the most risky link.
In the prior art, in order to ensure the quality of part of medical medicines and medical apparatuses with high requirements for low-temperature storage, the medicines and the medical apparatuses are usually placed in a low-temperature refrigerator car for transportation, but the transportation mode is extremely easily influenced by the external environment, the performance in the refrigerator car, the object transfer process, human negligence and the like, the medicines and the medical apparatuses are difficult to be ensured to be always kept in the specified low-temperature storage environment in the transportation process, and the storage of part of the medicines sensitive to temperature is not facilitated; at present often through the auxiliary usage with the help of ice bag to maintain its low temperature environment, but maintain the effect limited, and be unfavorable for used repeatedly, environmental load is big, in addition, the phenomenon that some medical medicine received impact damage in the transfer process appears easily.
Therefore, the existing ice bag has the problems of poor continuity of low-temperature effect, inconvenience for repeated use, large environmental load and easiness in causing impact damage to medical articles.
Disclosure of Invention
The embodiment of the invention aims to provide a medical packaging film, and aims to solve the problems that the existing ice bag is poor in low-temperature effect continuity, not beneficial to repeated use, large in environmental load and easy to impact and damage medical articles.
The embodiment of the invention is realized in such a way that the medical packaging film comprises an inner film layer, an outer film layer and a phase change energy storage material which is packaged between the outer film layer and the inner film layer;
wherein the outer film layer comprises the following raw materials in parts by weight:
65-80 parts of polylactide, 3-9 parts of polybutylene succinate, 4-8 parts of nanocellulose and 3-8 parts of ethylene isophthalate;
the inner film layer comprises the following raw materials in parts by weight:
65-80 parts of polylactic acid-glycollic acid copolymer, 8-12 parts of zinc chloride solution, 4-8 parts of nano cellulose, 4-8 parts of calcium propionate and 0.5-5 parts of polyethylene glycol terephthalate;
the phase-change energy storage material is prepared from a sodium chloride solution, starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin according to the weight ratio of 1: (3-5): (2-4): (0.01-0.03) by mixing.
Another object of an embodiment of the present invention is to provide a method for preparing the medical packaging film, including the following steps:
weighing raw materials according to the raw material formulas of the outer membrane layer and the inner membrane layer, uniformly mixing the raw materials of the membrane layers, preparing the outer membrane layer into a smooth membrane, and preparing the inner membrane layer into an arched membrane;
and filling the phase change energy storage material into the arched membrane, and then placing the leveling membrane above the arched membrane to perform hot press molding with the arched membrane, so as to obtain the phase change energy storage material.
The medical packaging film provided by the embodiment of the invention is formed by combining an inner film layer, an outer film layer and a phase-change energy storage material packaged between the outer film layer and the inner film layer, wherein the outer film layer is prepared by taking polylactide, polybutylene succinate, nanocellulose and ethylene glycol isophthalate as raw materials, and the inner film layer is prepared by taking polylactic acid-glycolic acid copolymer, a zinc chloride solution, nanocellulose, calcium propionate and polyethylene glycol terephthalate as raw materials, and the raw materials are wide in source, green and environment-friendly, and have degradability, excellent barrier property, mechanical property and high transparency; in addition, the phase-change energy storage material consisting of sodium chloride solution, starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin is packaged between the outer film layer and the inner film layer, so that the cold storage effect is good and lasting, the repeated utilization rate is high, and compared with the traditional packaging mode, the medical packaging film formed by combining the inner film layer, the outer film layer and the phase-change energy storage material packaged between the outer film layer and the inner film layer can protect medical articles to a certain degree.
Drawings
Fig. 1 is a schematic structural diagram of a medical packaging film provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The traditional solution in the ice bag is mainly aqueous solution or supplemented with highly toxic substances such as borax and the like, wherein the solid shape of the aqueous solution is difficult to fix due to the high fluidity of the aqueous solution, hard solid edges and corners are particularly easy to form to damage external packaging materials, and certain potential impact damage hazards exist on packaged objects. In addition, the latent heat of phase change of water is small, the cold accumulation effect is limited, and the reuse is not facilitated. In order to solve the problems that the existing ice bag has poor continuity of low-temperature effect, is not beneficial to reuse, has large environmental load and is easy to cause impact damage to medical articles, the embodiment of the invention provides a medical packaging film, which is formed by combining an inner film layer, an outer film layer and a phase-change energy storage material packaged between the outer film layer and the inner film layer, wherein the outer film layer is prepared by taking polylactide, polybutylene succinate, nanocellulose and ethylene isophthalate as raw materials, and the inner film layer is prepared by taking polylactic acid-glycolic acid copolymer, a zinc chloride solution, nanocellulose, calcium propionate and polyethylene glycol terephthalate as raw materials; in addition, the phase-change energy storage material consisting of sodium chloride solution, starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin is packaged between the outer film layer and the inner film layer, the cold storage effect is good and lasting, the repeated utilization rate is high, and the medical packaging film formed by combining the inner film layer, the outer film layer and the phase-change energy storage material packaged between the outer film layer and the inner film layer can protect medical articles to a certain extent compared with the traditional packaging mode.
In the embodiment of the invention, as shown in fig. 1, the medical packaging film comprises an outer film layer 1, an inner film layer 2 and a phase change energy storage material 3 packaged between the outer film layer 1 and the inner film layer 2;
wherein, the outer film layer 1 comprises the following raw materials in parts by weight:
65-80 parts of polylactide, 3-9 parts of polybutylene succinate, 4-8 parts of nanocellulose and 3-8 parts of ethylene isophthalate;
the inner film layer 2 comprises the following raw materials in parts by weight:
65-80 parts of polylactic acid-glycollic acid copolymer, 8-12 parts of zinc chloride solution, 4-8 parts of nano cellulose, 4-8 parts of calcium propionate and 0.5-5 parts of polyethylene glycol terephthalate;
the phase-change energy storage material 3 is prepared from sodium chloride solution, starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin according to the weight ratio of 1: (3-5): (2-4): (0.01-0.03) by mixing.
In the embodiment of the invention, the phase-change energy storage material is subjected to physical state change during solid-solid phase change, solid-liquid phase change, solid-gas phase change and liquid-gas phase change, and absorbs heat from the environment during the phase change process, and releases heat to the environment. The energy that can be stored or released when a physical state changes is called phase transition heat, and the temperature range at which the phase transition occurs is narrow. When the physical state changes, the temperature of the material itself remains almost unchanged until the phase change is completed. A wide temperature plateau is created when a large amount of phase change heat is transferred to the environment. The phase-change energy storage material is prepared by compounding the raw materials of sodium chloride solution, starch water-absorbing resin, sodium polyacrylate and phase-change paraffin, and has high viscosity, gel-like property and biodegradability; experiments prove that when the mass fraction of the sodium chloride solution is 0.5-2%, the phase-change temperature of the phase-change energy storage material is-3 ℃ to-19.7 ℃, and the phase-change energy storage material is suitable for packaging medical articles with the temperature requirement of-1 ℃ to-16 ℃.
In a preferred embodiment of the present invention, the phase-change energy storage material is prepared from sodium chloride solution, starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin in a weight ratio of 1: 4: 3: 0.02 and mixing.
In the present example, the phase-change paraffin was purchased from ZJ-54, a product of Zhongjia New Material science and technology Co.
In an embodiment of the present invention, a preparation method of the starch-based water absorbent resin includes the following steps:
dropwise adding a mixed solution of sodium hydroxide and potassium hydroxide into acrylic acid until the pH value is 4-6 to obtain a standby solution;
adding gelatinized starch and an initiator into the standby solution, wherein the mass ratio of the standby solution to the gelatinized starch to the initiator is 35-70: 40-60: 1, stirring and heating under nitrogen atmosphere to carry out graft copolymerization reaction, and drying to obtain the product.
In the embodiment of the invention, the mixed solution of sodium hydroxide and potassium hydroxide is prepared by equivalent sodium hydroxide solution with the mass fraction of 25% and potassium hydroxide solution with the mass fraction of 25%.
In the embodiment of the invention, the gelatinized starch is obtained by stirring and gelatinizing corn starch and a proper amount of water at a constant temperature of 60-70 ℃ in advance, namely the content ratio of the starch to the water is not required to be strictly controlled, and the gelatinized starch can be added according to actual conditions only by the fact that the starch reaches the complete gelatinization degree.
In the embodiment of the invention, the initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate.
In addition, because a large amount of gas is easily generated in the phase change process, the volume change of the packaging material is large, and the requirements on the packaging material, such as strength, flexibility, thermal stability, heat transfer property, corrosion resistance, permeability resistance and the like, are severe. The packaging material adopted by the embodiment of the invention is composed of the outer film layer 1 and the inner film layer 2, the raw materials used by the film layers are wide in source and environment-friendly, the two layers have degradability, excellent barrier property, mechanical property and high transparency, in addition, in order to ensure the packaging effect, the thickness of each film layer is not less than 10 micrometers, the specific thickness is determined according to the actual situation, and no specific limitation is made herein.
In the examples of the present invention, polylactide, polybutylene succinate, ethylene isophthalate, polylactic acid-glycolic acid copolymer, and polyethylene terephthalate were obtained from the bio-technology corporation of the large, Jinan Dai.
In the embodiment of the invention, the preparation method of the nano-cellulose comprises the following steps:
placing natural cellulose pulp in a sulfuric acid solution for soaking treatment to obtain a first mixture;
placing the first mixture at the temperature of 40-60 ℃ for constant-temperature water bath treatment to obtain a second mixture;
and washing the second mixture to be neutral, and drying to obtain the catalyst.
Specifically, adding one or more of banana straws, corn straws and bagasse which are pulped to prepare natural cellulose pulp into a sulfuric acid solution with the mass fraction of 65% and the mass of the natural cellulose pulp being 9-11 times that of the natural cellulose pulp, soaking for 8-12 min, placing the natural cellulose pulp in a constant-temperature water bath reaction at the temperature of 40-60 ℃ for 100-110 min, taking out the natural cellulose pulp, washing the natural cellulose pulp to be neutral by deionized water, and drying for 40-50 h to obtain the nano-cellulose.
In the embodiment of the invention, the requirement on flexibility is higher when the inner film layer is contacted with the medical article, and the requirement on strength is higher when the outer film layer is contacted with the external environment; the preparation method comprises the following steps of firstly adopting a zinc chloride solution with the mass fraction of 55-65% to dissolve nano-cellulose in advance in the preparation process of the inner membrane layer, enabling zinc ions in the solution to have a certain weakening effect on hydrogen bonds forming the strength of the cellulose, further adding polylactic acid-glycolic acid copolymer, calcium propionate and polyethylene glycol terephthalate in a system, uniformly mixing, and promoting the formation of zinc-cellulose single chains in the system under the coordination effect of the calcium propionate.
In another preferred embodiment of the present invention, the outer film layer comprises the following raw materials by weight:
70-75 parts of polylactide, 5-7 parts of polybutylene succinate, 5-7 parts of nanocellulose and 4-7 parts of ethylene isophthalate;
the inner film layer comprises the following raw materials in parts by weight:
70-75 parts of polylactic acid-glycollic acid copolymer, 9-11 parts of zinc chloride solution, 5-7 parts of nano cellulose, 5-7 parts of calcium propionate and 1-3 parts of polyethylene terephthalate.
In another preferred embodiment of the present invention, the outer film layer comprises the following raw materials by weight:
72.5 parts of polylactide, 6 parts of polybutylene succinate, 6 parts of nanocellulose and 5.5 parts of ethylene isophthalate;
the inner film layer comprises the following raw materials in parts by weight:
72.5 parts of polylactic acid-glycolic acid copolymer, 10 parts of zinc chloride solution, 6 parts of nano cellulose, 6 parts of calcium propionate and 2 parts of polyethylene terephthalate.
The invention provides a preparation method of the medical packaging film, which comprises the following steps:
weighing raw materials according to the raw material formulas of the outer membrane layer and the inner membrane layer, uniformly mixing the raw materials of the membrane layers, preparing the outer membrane layer into a smooth membrane, and preparing the inner membrane layer into an arched membrane;
and filling the phase change energy storage material into the arched membrane, and then placing the leveling membrane above the arched membrane to perform hot press molding with the arched membrane, so as to obtain the phase change energy storage material.
Wherein, the hot-press forming is the prior conventional technical means. The flattening film is made of a conventional flattening mold and the arched film is made of a conventional arched grinding tool. The arch-shaped film is in an even concave-convex fluctuation state after being formed, the concave part is filled with the phase-change energy storage material, but the phase-change energy storage material is not excessively filled, and the phase-change energy storage material can occupy 60-70% of the volume of the concave part, so that on one hand, a subsequent forming effect is ensured, and on the other hand, a certain buffering effect is provided for medical articles, and the collision and abrasion conditions are reduced.
The medical packaging film and the preparation method thereof of the present invention are further described with reference to the following specific examples, but the specific implementation methods mentioned in these examples are only illustrative and explanatory of the technical solution of the present invention, and do not limit the implementation scope of the present invention, and all modifications and substitutions based on the above principles should be within the protection scope of the present invention.
The starch-based water-absorbent resins and nanocelluloses used in the following examples were prepared by themselves, and the rest of polylactide, polybutylene succinate, ethylene isophthalate, polylactic acid-glycolic acid copolymer, zinc chloride, calcium propionate, polyethylene terephthalate, sodium chloride, starch-based water-absorbent resins, sodium polyacrylate, and phase-change paraffin were all commercially available.
Wherein, the starch water-absorbing resin is prepared by the following steps: dripping a mixed solution of sodium hydroxide and potassium hydroxide into a certain amount of acrylic acid until the pH value is 5 to obtain a standby solution; adding gelatinized corn starch and potassium persulfate into the standby solution, wherein the mass ratio of the standby solution to the gelatinized starch to the initiator is 55: 50: 1, stirring and heating in a nitrogen atmosphere to perform graft copolymerization reaction for 1h, stopping introducing nitrogen, and placing in an oven to dry at 100 ℃ to obtain the graft copolymerization product.
Wherein, the nano-cellulose is prepared by the following steps: adding natural cellulose pulp prepared by pulping banana straws into a sulfuric acid solution with the mass fraction of 65% and the mass of the natural cellulose pulp being 10 times that of the natural cellulose pulp, soaking for 10min, then placing the natural cellulose pulp at the temperature of 50 ℃ for constant-temperature water bath reaction for 105min, taking out the natural cellulose pulp, washing the natural cellulose pulp to be neutral by using deionized water, and drying for 45h to obtain the banana straw pulp.
Example 1
Weighing the raw materials according to the raw material formula of the outer film layer, wherein the outer film layer comprises the following raw materials in parts by weight: 65.5 parts of polylactide, 3.8 parts of polybutylene succinate, 4.2 parts of nano-cellulose and 3 parts of ethylene isophthalate; uniformly mixing the polylactide, the polybutylene succinate, the nanocellulose and the ethylene isophthalate, and preparing an outer membrane layer into a flat membrane;
weighing the raw materials according to the raw material formula of the inner film layer, wherein the inner film layer comprises the following raw materials in parts by weight: 65.5 parts of polylactic acid-glycolic acid copolymer, 8.3 parts of zinc chloride solution with the mass fraction of 60%, 4.4 parts of nano cellulose, 4.5 parts of calcium propionate and 0.5 part of polyethylene terephthalate; uniformly mixing the polylactic acid-glycolic acid copolymer, a zinc chloride solution with the mass fraction of 60%, nano-cellulose, calcium propionate and polyethylene glycol terephthalate, and preparing an inner membrane layer into an arched membrane;
1 percent of sodium chloride solution, starch water-absorbing resin, sodium polyacrylate and phase-change paraffin by weight percent of 1: 3: 2: 0.01 to obtain a phase change energy storage material, filling the phase change energy storage material into the arched film, and then placing a leveling film above the arched film to carry out hot press molding with the arched film, thus obtaining the medical packaging film.
Example 2
Weighing the raw materials according to the raw material formula of the outer film layer, wherein the outer film layer comprises the following raw materials in parts by weight: 79 parts of polylactide, 8.5 parts of polybutylene succinate, 7.4 parts of nanocellulose and 7.5 parts of ethylene isophthalate; uniformly mixing the polylactide, the polybutylene succinate, the nanocellulose and the ethylene isophthalate, and preparing an outer membrane layer into a flat membrane;
weighing the raw materials according to the raw material formula of the inner film layer, wherein the inner film layer comprises the following raw materials in parts by weight: 79.8 parts of polylactic acid-glycolic acid copolymer, 11.8 parts of zinc chloride solution with the mass fraction of 60%, 8 parts of nano cellulose, 7.8 parts of calcium propionate and 5 parts of polyethylene terephthalate; uniformly mixing the polylactic acid-glycolic acid copolymer, a zinc chloride solution with the mass fraction of 60%, nano-cellulose, calcium propionate and polyethylene glycol terephthalate, and preparing an inner membrane layer into an arched membrane;
1 percent of sodium chloride solution, starch water-absorbing resin, sodium polyacrylate and phase-change paraffin by weight percent of 1: 4: 3: 0.03, filling the phase change energy storage material in the arched film, and then placing the leveling film above the arched film to perform hot press molding with the arched film, thus obtaining the medical packaging film.
Example 3
Weighing the raw materials according to the raw material formula of the outer film layer, wherein the outer film layer comprises the following raw materials in parts by weight: 70.2 parts of polylactide, 5.5 parts of polybutylene succinate, 5.5 parts of nanocellulose and 4.6 parts of ethylene isophthalate; uniformly mixing the polylactide, the polybutylene succinate, the nano-cellulose and the ethylene isophthalate, and preparing an outer membrane layer into a leveling membrane;
weighing the raw materials according to the raw material formula of the inner film layer, wherein the inner film layer comprises the following raw materials in parts by weight: 70.7 parts of polylactic acid-glycolic acid copolymer, 9.5 parts of zinc chloride solution, 5.2 parts of nano cellulose, 5.7 parts of calcium propionate and 1 part of polyethylene terephthalate; uniformly mixing the polylactic acid-glycolic acid copolymer, a zinc chloride solution with the mass fraction of 60%, nano-cellulose, calcium propionate and polyethylene glycol terephthalate, and preparing an inner membrane layer into an arched membrane;
1 percent of sodium chloride solution, starch water-absorbing resin, sodium polyacrylate and phase-change paraffin by weight percent of 1: 5: 2: 0.02 mixing to obtain a phase change energy storage material, filling the phase change energy storage material into the arched film, and then placing the leveling film above the arched film to perform hot press molding with the arched film to obtain the medical packaging film.
Example 4
Weighing the raw materials according to the raw material formula of the outer film layer, wherein the outer film layer comprises the following raw materials in parts by weight: 74.5 parts of polylactide, 6.8 parts of polybutylene succinate, 7.8 parts of nanocellulose and 8 parts of ethylene isophthalate; uniformly mixing the polylactide, the polybutylene succinate, the nanocellulose and the ethylene isophthalate, and preparing an outer membrane layer into a flat membrane;
weighing the raw materials according to the raw material formula of the inner film layer, wherein the inner film layer comprises the following raw materials in parts by weight: 74.3 parts of polylactic acid-glycolic acid copolymer, 10.4 parts of zinc chloride solution with the mass fraction of 60%, 6.1 parts of nano-cellulose, 6.5 parts of calcium propionate and 2 parts of polyethylene terephthalate; uniformly mixing the polylactic acid-glycolic acid copolymer, a zinc chloride solution with the mass fraction of 60%, nano-cellulose, calcium propionate and polyethylene glycol terephthalate, and preparing an inner membrane layer into an arched membrane;
1 percent of sodium chloride solution, starch water-absorbing resin, sodium polyacrylate and phase-change paraffin by weight percent of 1: 3: 2: 0.01 to obtain a phase change energy storage material, and after the phase change energy storage material is filled in the arched film, the leveling film is placed above the arched film to be hot-pressed and molded with the arched film, so that the medical packaging film is obtained.
Example 5
Weighing the raw materials according to the raw material formula of the outer film layer, wherein the outer film layer comprises the following raw materials in parts by weight: 72.5 parts of polylactide, 6 parts of polybutylene succinate, 6 parts of nanocellulose and 5.5 parts of ethylene isophthalate; uniformly mixing the polylactide, the polybutylene succinate, the nanocellulose and the ethylene isophthalate, and preparing an outer membrane layer into a flat membrane;
weighing the raw materials according to the raw material formula of the inner film layer, wherein the inner film layer comprises the following raw materials in parts by weight: 72.5 parts of polylactic acid-glycolic acid copolymer, 10 parts of zinc chloride solution, 6 parts of nano cellulose, 6 parts of calcium propionate and 2 parts of polyethylene terephthalate; uniformly mixing the polylactic acid-glycolic acid copolymer, a zinc chloride solution with the mass fraction of 60%, nano-cellulose, calcium propionate and polyethylene glycol terephthalate, and preparing an inner membrane layer into an arched membrane;
1 percent of sodium chloride solution, starch water-absorbing resin, sodium polyacrylate and phase-change paraffin by weight percent of 1: 4: 3: 0.02 mixing to obtain a phase change energy storage material, filling the phase change energy storage material into the arched film, and then placing the leveling film above the arched film to perform hot press molding with the arched film to obtain the medical packaging film.
The inner film layer in the medical packaging film prepared in the embodiments 1 to 5 of the present invention and the commercially available medical packaging film (PET film) are subjected to the related tests of the elastic modulus, the elongation at break and the biodegradation rate, and the specific test method can refer to the test method of the tensile property of the national drug package standard (YBB00112003-2015) and the test method according to ISO: 14855 the biodegradation rate test was carried out with the relevant test methods and the specific test results are shown in table 1.
TABLE 1
As can be seen from table 1, the inner film layers of the medical packaging films prepared in examples 1 to 5 of the present invention all have good flexibility, which is equivalent to that of the commercially available medical packaging film (PET film), and the biodegradability of the medical packaging film is as high as 70% or more, which is superior to that of the currently commercially available PET film. According to the embodiment of the invention, the nano-cellulose is dissolved in advance by using the zinc chloride solution, so that zinc ions in the solution generate a certain weakening effect on hydrogen bonds forming the strength of the cellulose, and then the polylactic acid-glycolic acid copolymer, the calcium propionate and the polyethylene glycol terephthalate are added into the system and uniformly mixed, and the formation of zinc-cellulose single chains in the system is promoted under the coordination effect of the calcium propionate, so that the formed inner film layer not only has degradability, but also has high transparency.
Further, the requirement on strength is high due to the fact that the outer film layer is in contact with the external environment, the outer film layer in the medical packaging film prepared in the embodiment 1-5 and a commercially available ice bag packaging film are tested for mechanical property and biodegradation rate, wherein the tensile strength is tested according to a testing method in GB/T1040.1-2006; the tear strength was tested according to test method in GB/T1040.1-2006, the test results are shown in Table 2 below.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Ice bag on market | |
| Tensile strength (Mpa) | 56 | 58 | 61 | 72 | 77 | 21 |
| Tear Strength (N) | 129 | 137 | 127 | 145 | 149 | 102 |
| Biodegradation Rate (%) | 81 | 79 | 77 | 82 | 85 | Is not degradable |
In summary, as can be seen from table 2, the outer film layer of the medical packaging films prepared in examples 1 to 5 of the present invention not only has high transparency, but also has significantly superior tensile strength and tear strength compared to the commercially available ice bag packaging films, and the biodegradation rate is as high as 75% or more. In addition, in the earlier development process of the present invention, it is determined that the adding proportion of the nanocellulose component in the outer film layer and the inner film layer in the system plays a key role in the improvement of the transparency, the barrier property and the mechanical property thereof, the following is to perform a gas permeation test on the inner film layer and the outer film layer in the medical packaging films prepared in the embodiments 1 to 5 of the present invention and the existing commercially available EVOH high barrier membrane, the test results are shown in table 3, and the test method refers to "national drug package standard gas permeation quantity determination method" (YBB 00082003-2015).
TABLE 3
From table 3, it is understood that the gas transmission rates of the inner film layer and the outer film layer of the medical packaging films prepared in examples 1 to 5 of the present invention are both lower than those of commercially available EVOH high barrier films, i.e., the films are more protective against medical articles, and can further prevent medical articles from being deteriorated or worn. It is noted that when the content of the nanocellulose in the system is too low or too high (e.g. the content of the nanocellulose in the inner film layer is less than 3.5% or more than 9.5% by mass, and the content of the nanocellulose in the outer film layer is less than 3.9% or more than 11% by mass), the barrier property and the mechanical property are reduced.
Further, the phase change latent heat test in the phase change generation process is performed on the phase change energy storage material and water in the medical packaging film prepared in the embodiments 1 to 5 of the present invention by differential scanning calorimetry, the test results are shown in table 4, the medical packaging film prepared in the embodiments 1 to 5 of the present invention and a commercially available ice bag are respectively subjected to temperature control packaging on the medical drug insulin, the packaging mode is consistent, the refrigeration transportation simulation test is performed, other conditions in the test process are controlled to be consistent, the simulated refrigeration transportation time is 24 hours, the temperature of the medical drug insulin sample is respectively measured and recorded before and after the test is completed, the temperature test is performed by inserting a thermometer into the insulin, the temperature value is recorded after the temperature change is stable, and the test results are shown in table 5.
TABLE 4
TABLE 5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Ice bag on market | |
| Before test (. degree.C.) | 1.5 | 1.2 | 1.7 | 1.3 | 1.2 | 1.3 |
| After test (. degree. C.) | 1.8 | 1.4 | 1.6 | 1.4 | 1.2 | 6.8 |
| Value of change in temperature | +0.3 | +0.2 | -0.1 | +0.1 | 0 | +5.3 |
In summary, as can be seen from table 4, the phase change latent heat of the phase change energy storage material in the medical packaging films prepared in embodiments 1 to 5 of the present invention is significantly greater than the phase change latent heat of water, and the energy storage effect is excellent; as can be seen from table 5, the medical packaging films prepared in embodiments 1 to 5 of the present invention have better cold accumulation and heat preservation effects compared to the commercially available ice bags, and can keep the temperature of the medicine relatively constant, thereby further preventing medical articles from deteriorating or being worn; in addition, the addition of the starch water-absorbent resin and the sodium polyacrylate component in the phase-change energy storage material has certain influence on the cold accumulation and heat preservation effect of the system, in particular, in the early development process of the invention, other commercially available starch water-absorbent resins are also adopted, but the cold accumulation and heat preservation effect of the prepared phase-change energy storage material is not as good as that of the potassium-containing starch water-absorbent resin prepared by grafting sodium acrylate and potassium acrylate onto starch, and when the sodium polyacrylate component is not contained in the system, the cold accumulation and heat preservation effect of the prepared phase-change material is obviously reduced.
To sum up, the medical packaging film provided by the embodiment of the invention is composed of an inner film layer, an outer film layer and a phase change energy storage material packaged between the outer film layer and the inner film layer, wherein the outer film layer is prepared by taking polylactide, polybutylene succinate, nanocellulose and ethylene glycol isophthalate as raw materials, and the inner film layer is prepared by taking polylactic acid-glycolic acid copolymer, a zinc chloride solution, nanocellulose, calcium propionate and polyethylene glycol terephthalate as raw materials, and the raw materials are wide in source, green and environment-friendly, and have degradability, excellent barrier property, mechanical property and high transparency; in addition, the phase-change energy storage material consisting of sodium chloride solution, starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin is packaged between the outer film layer and the inner film layer, the cold storage effect is good and lasting, the repeated utilization rate is high, and the medical packaging film formed by combining the inner film layer, the outer film layer and the phase-change energy storage material packaged between the outer film layer and the inner film layer can protect medical articles to a certain extent compared with the traditional packaging mode.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The medical packaging film is characterized by comprising an outer film layer, an inner film layer and a phase change energy storage material packaged between the outer film layer and the inner film layer;
wherein the outer film layer comprises the following raw materials in parts by weight:
65-80 parts of polylactide, 3-9 parts of polybutylene succinate, 4-8 parts of nanocellulose and 3-8 parts of ethylene isophthalate;
the inner film layer comprises the following raw materials in parts by weight:
65-80 parts of polylactic acid-glycollic acid copolymer, 8-12 parts of zinc chloride solution, 4-8 parts of nano cellulose, 4-8 parts of calcium propionate and 0.5-5 parts of polyethylene glycol terephthalate;
the phase-change energy storage material is prepared from a sodium chloride solution, starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin according to the weight ratio of 1: (3-5): (2-4): (0.01-0.03) mixing;
the preparation method of the starch water-absorbent resin comprises the following steps:
dropwise adding a mixed solution of sodium hydroxide and potassium hydroxide into acrylic acid until the pH value is 4-6 to obtain a standby solution;
adding gelatinized starch and an initiator into the standby solution, wherein the mass ratio of the standby solution to the gelatinized starch to the initiator is 35-70: 40-60: 1, stirring and heating under nitrogen atmosphere to carry out graft copolymerization reaction, and drying to obtain the product.
2. The medical packaging film according to claim 1, wherein the phase-change energy storage material is prepared from a sodium chloride solution, a starch-based water-absorbing resin, sodium polyacrylate and phase-change paraffin according to a weight ratio of 1: 4: 3: 0.02 and mixing.
3. The medical packaging film of claim 1, wherein the initiator is one of potassium persulfate, sodium persulfate, and ammonium persulfate.
4. The medical packaging film according to claim 1, wherein the mass fraction of the sodium chloride solution is 0.5% -2%.
5. The medical packaging film according to claim 1, wherein the mass fraction of the zinc chloride solution is 55-65%.
6. The medical packaging film according to claim 1, wherein the nanocellulose is prepared by a method comprising:
placing natural cellulose pulp in a sulfuric acid solution for soaking treatment to obtain a first mixture;
placing the first mixture at the temperature of 40-60 ℃ for constant-temperature water bath treatment to obtain a second mixture;
and (4) washing the second mixture to be neutral, and drying to obtain the catalyst.
7. The medical packaging film of claim 1, wherein the outer film layer comprises the following raw materials in parts by weight:
70-75 parts of polylactide, 5-7 parts of polybutylene succinate, 5-7 parts of nanocellulose and 4-7 parts of ethylene isophthalate;
the inner film layer comprises the following raw materials in parts by weight:
70-75 parts of polylactic acid-glycollic acid copolymer, 9-11 parts of zinc chloride solution, 5-7 parts of nano cellulose, 5-7 parts of calcium propionate and 1-3 parts of polyethylene terephthalate.
8. The medical packaging film of claim 1, wherein the outer film layer comprises the following raw materials in parts by weight:
72.5 parts of polylactide, 6 parts of polybutylene succinate, 6 parts of nanocellulose and 5.5 parts of ethylene isophthalate;
the inner film layer comprises the following raw materials in parts by weight:
72.5 parts of polylactic acid-glycolic acid copolymer, 10 parts of zinc chloride solution, 6 parts of nano cellulose, 6 parts of calcium propionate and 2 parts of polyethylene terephthalate.
9. A method for preparing the medical packaging film according to any one of claims 1 to 8, wherein the method comprises the following steps:
weighing raw materials according to the raw material formula of the outer film layer and the inner film layer of any one of claims 1 to 8, uniformly mixing the raw materials of the film layers, making the outer film layer into a flat film, and making the inner film layer into an arched film;
and filling the phase change energy storage material into the arched membrane, and then placing the leveling membrane above the arched membrane to perform hot press molding with the arched membrane, thus obtaining the phase change energy storage material.
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