阅读说明：本技术 抑菌膜及其制备方法与应用 (Antibacterial film and preparation method and application thereof ) 是由 马骏 李文宇 左玉星 于 2021-11-25 设计创作，主要内容包括：本发明涉及膜材料技术领域,公开了抑菌膜及其制备方法和应用。抑菌膜包括抗菌缓释层,抗菌缓释层的制备原料按重量份数计包括：0.4～2份抗菌母粒、10～20份可降解材料以及68～88.6份基材树脂,抗菌缓释层是由制备原料混合均匀制膜得到；抗菌母粒是由抗菌剂和与基材树脂具有相容性的造粒树脂混合造粒得到。抑菌膜的制备方法,包括将上述制备原料混合制膜。该抑菌膜具有抑菌效果长效稳定,抑菌效果好的特点,可应用在医疗、日化、家电、纺织或食品包装等领域中,特别是可应用于植入消化道的医疗材料中。(The invention relates to the technical field of membrane materials, and discloses a bacteriostatic membrane as well as a preparation method and application thereof. The antibacterial film comprises an antibacterial slow-release layer, and the antibacterial slow-release layer is prepared from the following raw materials in parts by weight: 0.4-2 parts of antibacterial master batch, 10-20 parts of degradable material and 68-88.6 parts of base material resin, wherein the antibacterial slow release layer is prepared by uniformly mixing preparation raw materials and preparing a film; the antibacterial master batch is obtained by mixing and granulating an antibacterial agent and a granulating resin which is compatible with the base material resin. The preparation method of the antibacterial film comprises the step of mixing the preparation raw materials to prepare the film. The antibacterial film has the characteristics of long-acting and stable antibacterial effect and good antibacterial effect, can be applied to the fields of medical treatment, daily chemicals, household appliances, textile or food packaging and the like, and particularly can be applied to medical materials implanted into the digestive tract.)

1. The bacteriostatic film is characterized by comprising an antibacterial sustained-release layer, wherein the antibacterial sustained-release layer is prepared from the following raw materials in parts by weight: 0.4-2 parts of antibacterial master batch, 10-20 parts of degradable material and 68-88.6 parts of base material resin, wherein the antibacterial slow release layer is prepared by uniformly mixing the preparation raw materials and preparing a film;

the antibacterial master batch is obtained by mixing and granulating an antibacterial agent and a granulating resin which is compatible with the base material resin.

2. The bacteriostatic film according to claim 1, wherein the degradable material comprises at least one of polylactic acid, PBAT and PVA; preferably, the degradable material is polylactic acid.

3. The bacteriostatic film according to claim 2, wherein the base resin is polyethylene resin, the raw materials for preparing the antibacterial sustained-release layer comprise 1-10 parts by weight of a compatilizer, and the compatilizer comprises at least one of ethylene-methacrylic acid-glycidyl methacrylate and LLDPE grafted glycidyl methacrylate-styrene copolymer;

preferably, the substrate resin is at least one of LDPE, LLDPE, HDPE and mPE;

more preferably, the pelletizing resin is at least one of LDPE, LLDPE, HDPE and mPE.

4. The antibacterial film according to claim 1, wherein the mass ratio of the antibacterial agent in the antibacterial master batch to the granulating resin is 1: 5-12;

preferably, the antibacterial agent includes a metal ion type antibacterial agent and a metal oxide type antibacterial agent;

more preferably, the metal ion-based antibacterial agent includes at least one of a silver ion-based antibacterial agent, a copper ion-based antibacterial agent, and a zinc ion-based antibacterial agent; more preferably, the metal oxide-based antibacterial agent includes at least one of a silver oxide-based antibacterial agent, a copper oxide-based antibacterial agent, a magnesium oxide-based antibacterial agent, a zinc oxide-based antibacterial agent, and a calcium oxide-based antibacterial agent;

further preferably, the antibacterial agent is at least one selected from the group consisting of a silver ion antibacterial agent whose carrier is glass beads, a silver ion antibacterial agent whose carrier is a zirconium phosphate salt, and nano zinc oxide.

5. The antibacterial film according to claim 1, wherein the substance mixed with the antibacterial agent and the granulating resin for granulation further comprises a dispersing agent, and the dispersing agent accounts for 0.5-2% of the mass of the antibacterial master batch;

preferably, the dispersant includes at least one of zinc stearate, polyethylene wax, and paraffin wax.

6. The bacteriostatic film according to any one of claims 1 to 5, which is a multilayer structure and comprises a corona layer and at least one antibacterial slow-release layer positioned on the surface of the bacteriostatic film;

preferably, the antibacterial slow-release layer is divided into two layers, namely a core layer and a heat-sealing layer, and the core layer and the heat-sealing layer are sequentially connected with the corona layer.

7. A preparation method of the antibacterial film, which is used for preparing the antibacterial film as claimed in any one of claims 1 to 5, and comprises the step of mixing the preparation raw materials to prepare the film.

8. The method of claim 7, wherein the film is formed by casting or coextrusion blowing.

9. The application of the bacteriostatic film according to any one of claims 1 to 6 in the fields of medical treatment, household appliances, textiles, daily chemicals or food packaging.

10. Use of an antibacterial film according to any one of claims 1 to 6 in a medical material for implantation into the digestive tract.

Technical Field

The invention relates to the technical field of membrane materials, in particular to a bacteriostatic membrane and a preparation method and application thereof.

Background

With the concern of people on good life and health, the antibacterial material is widely applied to the industries of medical treatment, household appliances, textile, daily chemicals, food, packaging and the like. The antibacterial plastic film is prepared by dispersing and adding an antibacterial material into a film forming material, modifying the film forming material to enable the film forming material to have certain antibacterial performance, and processing the film forming material by processes of blow molding, tape casting and the like. Common antibacterial materials include organic natural materials, organic synthetic materials and inorganic materials, and the antibacterial materials are also classified into dissoluble antibacterial materials and non-dissoluble antibacterial materials according to the use requirements. Products with higher safety requirements generally adopt non-dissoluble antibacterial materials, the non-dissoluble antibacterial materials inhibit the growth of bacteria in a contact mode, the commonly used antibacterial materials are metal ion bacteriostats, but after the metal ions contact, if a bacterial corpse is covered, the continuous sterilization is prevented, and the lasting antibacterial effect is not ideal; meanwhile, long-term antibacterial is more challenging for applications in complex environments such as acid and alkali, mechanical friction, and the like, such as in the digestive tract.

The bacteriostatic plastic film in the prior art has the problems of fixed contact area of bacteriostatic materials and no lasting and stable bacteriostatic effect. Therefore, a bacteriostatic plastic film with stable bacteriostatic effect, strong durability and contact area is needed, and can be applied to the fields of medical treatment, outdoor and the like. Has good prospect for antibacterial application in the digestive tract in the medical field.

In view of this, the present application is specifically made.

Disclosure of Invention

The invention aims to provide a bacteriostatic film and a preparation method and application thereof.

The invention is realized by the following steps:

in a first aspect, the invention provides a bacteriostatic film, which comprises an antibacterial sustained-release layer, wherein the antibacterial sustained-release layer comprises the following preparation raw materials in parts by weight: 0.4-2 parts of antibacterial master batch, 10-20 parts of degradable material and 68-88.6 parts of base material resin, wherein the antibacterial slow release layer is prepared by uniformly mixing preparation raw materials and preparing a film;

the antibacterial master batch is obtained by mixing and granulating an antibacterial agent and a granulating resin which is compatible with the base material resin.

In an alternative embodiment, the degradable material comprises at least one of polylactic acid, PBAT and PVA; preferably, the degradable material is polylactic acid.

In an optional embodiment, the base material resin is polyethylene resin, the raw materials for preparing the antibacterial slow-release layer further comprise 1-10 parts by weight of a compatilizer, and the compatilizer comprises at least one of ethylene-methacrylic acid-glycidyl methacrylate and LLDPE grafted glycidyl methacrylate-styrene copolymer;

preferably, the substrate resin is at least one of LDPE, LLDPE, HDPE and mPE;

more preferably, the pelletizing resin is at least one of LDPE, LLDPE, HDPE and mPE.

In an optional embodiment, the mass ratio of the antibacterial agent in the antibacterial master batch to the granulating resin is 1: 5-12;

preferably, the antibacterial agent includes a metal ion type antibacterial agent and a metal oxide type antibacterial agent;

more preferably, the metal ion-based antibacterial agent includes at least one of a silver ion-based antibacterial agent, a copper ion-based antibacterial agent, and a zinc ion-based antibacterial agent; more preferably, the metal oxide-based antibacterial agent includes at least one of a silver oxide-based antibacterial agent, a copper oxide-based antibacterial agent, a magnesium oxide-based antibacterial agent, a zinc oxide-based antibacterial agent, and a calcium oxide-based antibacterial agent;

preferably, the antibacterial agent is at least one selected from the group consisting of a silver ion antibacterial agent with a carrier of glass beads, a silver ion antibacterial agent with a carrier of zirconium phosphate, and nano zinc oxide.

In an optional embodiment, the substance mixed with the antibacterial agent and the granulating resin for granulation further comprises a dispersing agent, wherein the dispersing agent accounts for 0.5-2% of the mass of the antibacterial master batch;

preferably, the dispersant includes at least one of zinc stearate, polyethylene wax, and paraffin wax.

In an alternative embodiment, the antibacterial film is a multilayer structure and comprises a corona layer and at least one antibacterial slow-release layer positioned on the surface of the antibacterial film;

preferably, the antibacterial slow-release layer is divided into two layers, namely a core layer and a heat-sealing layer, and the core layer and the heat-sealing layer are sequentially connected with the corona layer.

In a second aspect, the present invention provides a method for preparing a bacteriostatic film according to any one of the preceding embodiments, including mixing the raw materials for preparing the bacteriostatic film.

In an alternative embodiment, the film formation comprises cast film formation.

In an alternative embodiment, the antibacterial film is a multilayer structure, and the film making manner comprises multilayer co-extrusion blown film.

In a third aspect, the present invention provides a use of the bacteriostatic film according to any one of the preceding embodiments in the fields of medical treatment, home appliances, textiles, daily chemicals or food packaging.

In a fourth aspect, the present invention provides the use of a bacteriostatic membrane according to any one of the preceding embodiments in a medical material for implantation in the digestive tract.

The invention has the following beneficial effects:

the preparation raw materials of the antibacterial slow-release layer comprise a proper amount of degradable materials and antibacterial master batches, so that the degradable materials contained in the antibacterial slow-release layer of the antibacterial film are gradually degraded along with the lapse of time, the antibacterial master batches are gradually exposed, and the antibacterial agent is gradually exposed, so that the specific surface area of the antibacterial film is increased, the antibacterial effect is better, and the effect of continuously slowly releasing and inhibiting bacteria of the antibacterial film is achieved; and when the film is prepared, the antibacterial agent, the base resin and the degradable material are blended in the form of the antibacterial master batch to prepare the film, so that the problem of uneven dispersion caused by directly adding the antibacterial agent powder can be avoided, and continuous and stable bacteriostasis is further ensured.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a statistical chart of the growth of bacteria and fungi after the bacteria and fungi are inoculated on the 28-day antibacterial performance test of the bacteriostatic film provided in example 1;

fig. 2 is another statistical chart of the growth of bacteria and fungi after the bacteria and fungi are inoculated on the 28-day antibacterial performance test of the bacteriostatic film provided in example 1.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The bacteriostatic film provided by the embodiment of the present application, and the preparation method and application thereof are specifically described below.

The antibacterial film provided by the embodiment of the application comprises an antibacterial slow-release layer, and the preparation raw materials of the antibacterial slow-release layer comprise the following components in parts by weight: 0.4-2 parts of antibacterial master batch, 10-20 parts of degradable material and 68-88.6 parts of base material resin, wherein the antibacterial slow release layer is prepared by uniformly mixing preparation raw materials and preparing a film; the antibacterial master batch is obtained by mixing and granulating an antibacterial agent and a granulating resin which is compatible with the base material resin.

According to the antibacterial film provided by the embodiment of the application, as the preparation raw materials of the antibacterial slow-release layer comprise a proper amount of degradable materials and the antibacterial master batches, the degradable materials contained in the antibacterial slow-release layer of the antibacterial film are gradually degraded along with the lapse of time, the antibacterial master batches are gradually exposed, and then the antibacterial agent is gradually exposed, so that the specific surface area of the antibacterial film is increased, the antibacterial effect is better, and the effect of continuous slow-release and bacteriostasis of the antibacterial film is achieved; and because when the membrane is prepared, the antibacterial agent, the base resin and the degradable material are blended to prepare the membrane in the form of the antibacterial master batch, the problem of uneven dispersion caused by the direct addition of the antibacterial agent powder can be avoided, and the continuous, stable and better antibacterial effect is further ensured.

Preferably, in order to ensure a stable degradation rate of the antibacterial sustained-release layer, the degradable material includes at least one of polylactic acid, PBAT and PVA. The optimal degradation environments of different degradable materials are different, and generally speaking, the selection of the degradable materials depends on the use scene of the antibacterial film. Preferably, the degradable material is selected from polylactic acid with lower requirements on degradation conditions.

Preferably, in order to improve the compatibility of the degradable material and the base resin, the degradable material is more uniformly distributed in the base resin, and the stability of the connection with the base resin is better, so that the effects of reducing the degradation rate, enabling the degradable material to be stably and slowly degraded, and further enabling the antibacterial agent to be slowly and stably released are achieved. The base material resin is polyethylene resin, the raw materials for preparing the antibacterial slow-release layer further comprise 1-10 parts by weight of compatilizer, and the compatilizer comprises at least one of ethylene-methacrylic acid-glycidyl methacrylate (E-MA-GMA) and LLDPE grafted glycidyl methacrylate-styrene copolymer (LLDPE-g- (GMA-co-st)).

Specifically, the base material resin is at least one of LDPE, LLDPE, HDPE and mPE.

And in order to ensure that the compatibility between the antibacterial master batch and the base material resin is better and the connection between the antibacterial master batch and the base material resin is firmer, the granulating resin is at least one of LDPE, LLDPE, HDPE and mPE.

Preferably, in order to ensure a better antibacterial effect, the mass ratio of the antibacterial agent in the antibacterial master batch to the granulating resin is 1: 5-12.

Preferably, the antibacterial agent includes a metal ion type antibacterial agent and a metal oxide type antibacterial agent.

Specifically, the metal ion antibacterial agent comprises at least one of a silver ion antibacterial agent, a copper ion antibacterial agent and a zinc ion antibacterial agent; the metal oxide antibacterial agent includes at least one of silver oxide antibacterial agent, copper oxide antibacterial agent, magnesium oxide antibacterial agent, zinc oxide antibacterial agent and calcium oxide antibacterial agent.

Further, in order to ensure a better antibacterial effect, the antibacterial agent is at least one selected from a silver ion antibacterial agent with a carrier of glass beads, a silver ion antibacterial agent with a carrier of zirconium phosphate and nano zinc oxide.

Preferably, in order to make the antibacterial agent in the antibacterial mother particle uniformly dispersed in the mother particle, agglomeration of the powdery antibacterial agent is avoided. The substance mixed and granulated with the antibacterial agent and the granulating resin also comprises a dispersing agent, and the dispersing agent accounts for 0.5-2% of the mass of the antibacterial master batch.

Further, in order to obtain a better dispersion effect, the dispersing agent includes at least one of zinc stearate, polyethylene wax, and paraffin wax.

In a preferred embodiment, the antibacterial film is a multilayer structure and comprises a corona layer and at least one antibacterial slow-release layer positioned on the surface of the antibacterial film. The corona layer is obtained after corona treatment of the surface of the base film, so as to facilitate subsequent processing (such as gluing and the like).

Furthermore, the antibacterial slow-release layer is divided into two layers, namely a core layer and a heat-sealing layer, and the core layer and the heat-sealing layer are sequentially connected with the corona layer.

The multi-layer design of the antibacterial film is such as to impart various functions thereto, for example, increased strength, increased heat resistance, etc. A superficial layer of multilayer structure's antibacterial membrane is antibiotic slow-release layer all the time, and such design can make antibacterial membrane along with time, and degradable material is by outer to interior degradation gradually, thereby the antiseptic exposes and realizes stabilizing the slowly-releasing bacteriostat, and then reaches the stable effect that lasts for a long time antibacterial.

The preparation method of the antibacterial film provided by the embodiment of the application comprises the step of mixing the preparation raw materials mentioned in the above content to prepare the film.

The method specifically comprises the following steps:

s1 preparation of antibacterial masterbatch

Adding the granulation resin, the antibacterial agent and the dispersing agent into a high-speed mixer or an internal mixer according to the mixture ratio requirement, and extruding and granulating the mixture by a double-screw extruder to obtain the antibacterial master batch.

S2 film production

The antibacterial master batch, the base material resin, the compatilizer and the degradable material are uniformly mixed according to the proportioning requirement, and the antibacterial film is prepared by casting film or layer co-extrusion film blowing.

The antibacterial film provided by the embodiment of the application has a good continuous antibacterial effect, and can be widely applied to the fields of medical treatment, household appliances, textiles, daily chemicals, food or packaging. In particular, it can be used in medical materials implanted into the digestive tract.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

The utility model provides an antibacterial film, it has three layer construction, is corona layer, sandwich layer and heat-seal layer in proper order, and sandwich layer and heat-seal layer are antibiotic slow-release layer.

The antibacterial master batch in the core layer and the heat sealing layer comprises the following components in parts by weight: 1 part of silver ion antibacterial agent, 5 parts of LDPE and 0.03 part of zinc stearate.

The core layer and the heat sealing layer are all calculated according to the parts by weight: 0.4 part of antibacterial master batch, 10 parts of polylactic acid, 1 part of E-MA-GMA compatilizer and 88.6 parts of LDPE.

The resins used for the core layer and the heat sealing layer are Yangzi Basff 2420H resin and Maoming petrochemical 2426H resin respectively.

Example 2

The utility model provides an antibacterial film, it has three layer construction, is corona layer, sandwich layer and heat-seal layer in proper order, and sandwich layer and heat-seal layer are antibiotic slow-release layer.

The antibacterial master batch in the core layer and the heat sealing layer comprises the following components in parts by weight: 1 part of nano zinc oxide, 12 parts of mPE and 0.26 part of paraffin.

The core layer and the heat sealing layer are all calculated according to the parts by weight: 2 parts of antibacterial master batch, 20 parts of PVA, 10 parts of LLDPE-g- (GMA-co-st) compatilizer and 68 parts of LDPE.

The resins used for the core layer and the heat sealing layer are Yangzi Basff 2420H resin and Maoming petrochemical 2426H resin respectively.

Example 3

The utility model provides an antibacterial film, it has three layer construction, is corona layer, sandwich layer and heat-seal layer in proper order, and sandwich layer and heat-seal layer are antibiotic slow-release layer.

The antibacterial master batch in the core layer and the heat sealing layer comprises the following components in parts by weight: the carrier is 1 part of silver ion antibacterial agent of zirconium phosphate, 7 parts of LLDPE and 0.08 part of polyethylene wax.

The core layer and the heat sealing layer are all calculated according to the parts by weight: 1.5 parts of antibacterial master batch, 15 parts of polylactic acid, 8 parts of E-MA-GMA compatilizer and 75.5 parts of LLDPE.

The resins used for the core layer and the heat sealing layer are Yangzi Basff 2420H resin and Maoming petrochemical 2426H resin respectively.

Example 4

The application embodiment provides an antibacterial film, it has three layer construction, is corona layer and heat-seal layer in proper order, and the heat-seal layer is antibiotic slow-release layer.

The antibacterial master batch in the heat-sealing layer comprises the following components in parts by weight: 1 part of nano zinc oxide, 10 parts of HDPE and 0.11 part of polyethylene wax.

The heat-sealing layer comprises the following components in parts by weight: 1 part of antibacterial master batch, 15 parts of polylactic acid PBTA, 5 parts of LLDPE-g- (GMA-co-st) compatilizer and 79 parts of LLDPE.

The resins used for the core layer and the heat sealing layer are Yangzi Basff 2420H resin and Maoming petrochemical 2426H resin respectively.

Comparative example

This comparative example is essentially the same as example 1, except that the degradable material is completely replaced with LDPE resin.

Experimental example 1

The antibacterial films of example 1 and comparative example 1 are compounded with BOPP and AL to prepare an antibacterial bag, preservative-free mask liquid is contained in the bag, bacterial suspension of bacteria and fungi for test is added into the antibacterial bag mask liquid, 28-day antibacterial performance test is carried out, and logarithmic reduction values of antibacterial performance are respectively tested for 1 day, 7 days, 14 days and 28 days. The bacteriostatic effect of each experimental group is recorded in the following table 1, and the quality standard is shown in table 2. And the specific bacterial growth in example 1 is recorded in figures 1 and 2.

TABLE 1 record of bacteriostatic effect for each experimental group

As can be seen from the above table, the bacteriostatic effect of the bacteriostatic film provided by the example of the application on bacteria and fungi is better than that of the requirement of the United states pharmacopoeia USP38-NF33(2015) in chapter 51, while the bacteriostatic effect of the bacteriostatic film of the comparative example is inferior to that of the example of the application.

As can be seen from figures 1 and 2, after inoculation, most of fungi and bacteria basically have no existence on the 7 th day, and especially the killing effect on Candida albicans is most obvious, the embodiment of the application is better than the comparative example, which shows that the bacteriostatic film provided by the application has good bacteriostatic effect, no bacteria or fungi grow for 28 days, and shows that the bacteriostatic film has long-acting bacteriostatic effect.

Experimental example 2

The bacteriostatic membrane prepared in example 1 is placed in a simulated gastric juice environment, and the conditions are as follows: and testing the bacteriostatic effect of staphylococcus aureus and escherichia coli at 37 ℃/0-12 weeks, evaluating the colony log reduction value, and recording the result in the following table.

TABLE 2 statistics of experimental results in simulated gastric fluid

As can be seen from the table above, the antibacterial film provided by the embodiment of the application has a good antibacterial effect on staphylococcus aureus and escherichia coli in a simulated gastric juice environment, and is superior to the requirements of JIS Z2801: 2010.

Experimental example 3

The bacteriostatic membrane prepared in example 1 is placed in a simulated intestinal fluid environment, and the conditions are as follows: and testing the bacteriostatic effect of staphylococcus aureus and escherichia coli at 37 ℃/0-12 Week, and recording the results in the following table.

TABLE 3 statistics of experimental results in simulated intestinal fluids

As can be seen from the table above, the antibacterial film provided by the embodiment of the application has a good antibacterial effect on staphylococcus aureus and escherichia coli in a simulated intestinal fluid environment, and is superior to the requirements of JIS Z2801: 2010.

In summary, according to the antibacterial film provided by the application, as the preparation raw materials of the antibacterial sustained-release layer comprise a proper amount of the degradable material and the antibacterial master batch, the degradable material contained in the antibacterial sustained-release layer of the antibacterial film is gradually degraded along with the lapse of time, the antibacterial master batch is gradually exposed, and then the antibacterial agent is gradually exposed, so that the specific surface area of the antibacterial film is increased, the antibacterial effect is better, and the effect of continuously sustained-release and bacteriostasis of the antibacterial film is achieved; and when the film is prepared, the antibacterial agent, the base resin and the degradable material are blended in the form of the antibacterial master batch to prepare the film, so that the problem of uneven dispersion caused by directly adding the antibacterial agent powder can be avoided, and continuous and stable bacteriostasis is further ensured.

The preparation method of the antibacterial film can prepare the antibacterial film with good antibacterial effect and continuous and stable antibacterial effect, and the prepared antibacterial film can be applied to the fields of medical treatment, household appliances, textiles, daily chemicals, food packaging and the like, and especially can be applied to medical materials implanted into the digestive tract.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.