阅读说明：本技术 一种医用包装膜及其制备方法 (Medical packaging film and preparation method thereof ) 是由 汪向喜 于 2020-07-03 设计创作，主要内容包括：本发明适用材料技术领域,提供一种医用包装膜及其制备方法,包括外膜层、内膜层以及封装在所述外膜层与内膜层之间的相变蓄能材料；外膜层包括：聚丙交酯65～80份、聚丁二酸丁二醇酯3～9份、纳米纤维素4～8份以及间苯二甲酸乙二醇酯3～8份；内膜层包括：聚乳酸-乙醇酸共聚物65～80份、氯化锌溶液8～12份、纳米纤维素4～8份、丙酸钙4～8份以及聚对苯二甲酸乙二醇酯0.5～5份；相变蓄能材料是由氯化钠溶液、淀粉系吸水树脂、聚丙烯酸钠以及相变石蜡按照重量比例为1：(3～5)：(2～4)：(0.01～0.03)混合得到。本发明各膜层原料来源广泛、绿色环保,不仅具有可降解性,还具有优异的阻隔性能、力学性能以及高透明性,可对医用物品起保护作用,同时,相变蓄能材料的蓄冷效果好且持久,重复利用率高。(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.)

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) by mixing.

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 according to claim 1 or 2, wherein the preparation method of the starch-based water-absorbent resin comprises the steps of:

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.

4. The medical packaging film according to claim 3, wherein the initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate.

5. The medical packaging film according to claim 1, wherein the mass fraction of the sodium chloride solution is 0.5-2%.

6. The medical packaging film according to claim 1, wherein the mass fraction of the zinc chloride solution is 55-65%.

7. 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 washing the second mixture to be neutral, and drying to obtain the catalyst.

8. 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.

9. 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.

10. A method for preparing the medical packaging film according to any one of claims 1 to 9, 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 9, 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, so as to obtain the phase change energy storage material.

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.

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, 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.

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 in the phase change process, the material absorbs heat from the environment and releases heat to the environment. The energy that can be stored or released when a physical state changes is called phase change heat, and the temperature range at which phase change 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.