阅读说明：本技术 一种抑菌、防震、吸潮的可降解食品保鲜垫及其制备方法 (Antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad and preparation method thereof ) 是由 李立 李逸 康勇锋 施文正 樊敏 于 2019-11-21 设计创作，主要内容包括：本发明提供一种抑菌、防震、吸潮的可降解食品保鲜垫及其制备方法。所述抑菌、防震、吸潮的可降解食品保鲜垫的制备方法包括在抗菌PLA/淀粉发泡材料表面喷洒天然抗菌剂,再将抗菌PLA/淀粉发泡材料用打孔聚乳酸薄膜包覆,即得。本发明提供的保鲜垫具有内外双重抗菌效果,内部抗菌剂缓慢释放,外部抗菌剂通过挥发或与食品接触迅速发挥作用,兼顾了抗菌的时效性与长效性,具有广谱的抗菌能力,不仅可以抑制微生物的繁殖,减少食品腐败,延长产品储存期,还具有一定的吸水性和防震性,保证产品品质；同时本发明提供的保鲜垫又是一种绿色、安全、环境友好型的全生物可降解材料,具有十分广阔的应用前景。(The invention provides a degradable food fresh-keeping pad with the functions of bacteriostasis, shock resistance and moisture absorption and a preparation method thereof. The preparation method of the antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad comprises the steps of spraying a natural antibacterial agent on the surface of the antibacterial PLA/starch foaming material, and then coating the antibacterial PLA/starch foaming material with a perforated polylactic acid film to obtain the antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad. The freshness-keeping pad provided by the invention has dual antibacterial effects of inside and outside, the internal antibacterial agent is slowly released, the external antibacterial agent quickly plays a role by volatilization or contact with food, the antibacterial timeliness and long-acting property are both considered, the freshness-keeping pad has broad-spectrum antibacterial capability, not only can inhibit the reproduction of microorganisms, reduce the food spoilage and prolong the storage life of products, but also has certain water absorption and shock resistance, and the quality of the products is ensured; meanwhile, the freshness-retaining pad provided by the invention is a green, safe and environment-friendly full-biodegradable material, and has a very wide application prospect.)

1. A preparation method of a bacteriostatic, shockproof and moisture-absorbing degradable food fresh-keeping pad is characterized by comprising the steps of spraying a natural antibacterial agent on the surface of an antibacterial PLA/starch foaming material, and then coating the antibacterial PLA/starch foaming material with a perforated polylactic acid film.

2. The method for preparing the antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 1, wherein the antibacterial PLA/starch foaming material comprises the following raw materials in parts by weight: the composite material comprises, by weight, 75-85 parts of PLA, 15-25 parts of starch, 1-3 parts of HNTs-antibacterial agent composite material, 0.5-2 parts of foaming agent and 2-5 parts of compatibilizer.

3. The method for preparing the antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 2, wherein the method for preparing the antibacterial PLA/starch foaming material comprises the following steps:

(1) respectively drying PLA granules and starch, cooling and uniformly mixing to obtain mixed granules;

(2) mixing the foaming agent, the HNTs-antibacterial agent composite material and the compatibilizer, adding the mixture into the mixed particles, and uniformly stirring to obtain a mixed material;

(3) and adding the mixed material into a double-screw extruder, extruding and foaming, and cooling and shaping to obtain the antibacterial PLA/starch foaming material.

4. The method for preparing the bacteriostatic, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 2, wherein the HNTs-antibacterial agent composite material uses halloysite nanotubes as a carrier of an antibacterial agent, and the antibacterial agent comprises a nanoparticle antibacterial agent and/or an organic antibacterial agent.

5. The method for preparing the bacteriostatic, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 4, wherein the nano-particle antibacterial agent comprises nano Ag and nano TiO₂Nano ZnO, nano MgO and nano CaCO₃The organic antibacterial agent comprises one or more of gallic acid, sorbic acid, citral, p-anisic aldehyde and cinnamaldehyde.

6. The method for preparing the antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 2, wherein the compatibilizer is prepared from a plasticizer, a chain extender and a cross-linking agent 1: 1:1, the plasticizer is acetyl butyl citrate, the chain extender is glycidyl methacrylate, the cross-linking agent is citric acid and/or maleic anhydride, and the foaming agent is azodicarbonamide.

7. The method for preparing the bacteriostatic, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 1, wherein the natural antibacterial agent sprayed on the antibacterial PLA/starch foaming material is one or more of plant essential oil, chitosan, tea polyphenol, rosemary extract, potassium sorbate and lactic acid bacteria streptococci, and the plant essential oil comprises one or more of thyme essential oil, cinnamon essential oil and clove essential oil.

8. The method for preparing the antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 1, wherein the amount of the natural antibacterial agent is 1-3% of the mass of the antibacterial PLA/starch foaming material, and the natural antibacterial agent is prepared into a solution and then sprayed on the surface of the antibacterial PLA/starch foaming material.

9. The method for preparing the antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad according to claim 1, wherein the method for preparing the perforated polylactic acid film comprises the following steps: preparing a PLA film by casting PLA particles through a single-screw casting machine, and punching holes on the film by using a punching machine, wherein the diameter of each punching hole is 0.3-0.5 mm, and the density of each punching hole is 6-8 holes/cm²。

10. A degradable food fresh-keeping pad with functions of bacteriostasis, shock resistance and moisture absorption, which is prepared by the method of any one of claims 1-9.

Technical Field

The invention belongs to the technical field of foamed plastics, and particularly relates to a degradable food fresh-keeping pad with the functions of bacteriostasis, shock resistance and moisture absorption and a preparation method thereof.

Background

At present, the logistics transportation system in China is imperfect, and the preservation technology applied to the market is single. The ever-increasing contradiction between the insufficient, unmatched and incomplete fresh-keeping technical means of the fresh food production is gradually highlighted. Taking pork as an example, the 'Chinese pork circulation loss analysis' issued by the ministry of agriculture shows that the loss rates of the pork in three links of storage, transportation and sale are respectively 3.98%, 0.24% and 1.46%; for another example, the annual yield of fruits and vegetables in China exceeds 10 million tons, the loss rate is close to 20 percent, which is 5 times as high as that of developed countries, the loss and yield value of the fruits and vegetables is as high as 2000 million yuan, and the loss rate of fresh food in China is the first in the world.

In recent years, with the development of socioeconomic and the improvement of living standard, people pay more and more attention to the freshness and sanitary quality of food. Products with high freshness generally have short shelf life, are easy to decay and deteriorate due to microbial pollution, and have strict requirements on preservation conditions. Therefore, effective freshness-retaining measures must be taken to prevent such changes from occurring. The fresh-keeping pad is concerned by people due to the characteristics of convenience and effectiveness. Developing a food fresh-keeping pad with antibacterial, shockproof and moisture absorption functions, applying to the transportation and sale links of cold fresh meat and seafood, inhibiting the growth and propagation of microorganisms, adsorbing exuded juice and ensuring the product quality; the fruit and vegetable transportation method is applied to the transportation link of fruits and vegetables, reduces the spoilage of fruits and vegetables, relieves the damage of the fruits and vegetables caused by transportation bump, reduces the waste, and has very important social and economic benefits.

The foaming material has a plurality of excellent performances such as light weight, high impact strength, high specific strength, good heat and sound insulation, strong moisture absorption and the like, the density of the product can be reduced by adopting the foaming technology to prepare the fresh-keeping pad, and the foaming material has a certain buffering and shock-absorbing effect, is beneficial to the sale, transportation and storage of foods such as fruits and vegetables and the like, and provides convenience for consumers to store fresh meat.

Polylactic acid (PLA) is a biodegradable material with high strength and modulus, and is considered an environmentally friendly material with great potential. The polylactic acid foaming material has the characteristics of common foaming materials, and can be completely degraded. However, the pure polylactic acid foaming material has low foaming rate, poor cell morphology, uneven cell distribution and higher cost, so that the pure polylactic acid foaming material is difficult to have market competitiveness; in addition, PLA is in linear polymerization and has few side chain active groups, and the structural characteristics cause poor heat resistance and mechanical strength, so the application range is very limited.

The starch is a renewable resource which has wide source and low price, can be completely biodegraded, and has good foaming performance. The starch-based biodegradable foaming material is developed and replaces the traditional plastic foaming material, so that the petroleum resource can be saved, and the environmental friendliness of the product can be improved. The foaming material produced by using starch as a raw material also has certain water absorption, can adsorb juice exuded from meat and marine products, and is favorable for keeping the products fresh.

The research on starch and polylactic acid composite materials, two of the most potential green degradable polymers, has been already developed. The research aims to reduce the production cost and improve the interfacial compatibility of PLA/starch, thereby improving the mechanical property and finally replacing petroleum macromolecules on the market. There are currently three methods to improve the compatibility of the two: plasticizer modification, cross-linking agent modification and graft copolymer modification. The plasticizer modification is to modify starch into thermoplastic starch by adding the plasticizer, so that the toughness of the material is improved on one hand, and the PLA/starch compatibility is improved on the other hand; the modification of the cross-linking agent can play a role in chain extension, and the hydroxyl of the polylactic acid and the hydroxyl of the starch are connected through the reactant, so that the compatibility of the polylactic acid and the starch is improved, and the tensile strength of the material is improved; the graft copolymer modification is that PLA or degradable plastic with better compatibility with the PLA is grafted with starch to be used as a compatilizer of the PLA and the starch, so that the tensile strength of the graft copolymer is improved, and the elongation at break of the graft copolymer is improved.

Halloysite Nanotubes (HNTs) are a natural silicate material, often in the form of a multi-walled hollow tubular structure with open ends; has the performances of biocompatibility, relative hydrophobicity, good dispersibility, high adsorbability and the like, is an environment-friendly novel nano material, and is widely applied to a plurality of fields of drug carriers, sewage treatment, biological detection and the like. The HNTs has a nano hollow tubular structure, high specific surface area and high adsorbability, various particles can be easily loaded on the HNTs, and metal particles can be directly deposited on the outer surface or the inner cavity of the HNTs to prepare the nano composite material. Compared with other nano carrier materials, HNTs has low price, environmental protection, higher biocompatibility and mechanical strength, and is a novel low-cost controlled release carrier material.

The halloysite nanotube used as a carrier of the antibacterial agent has the following advantages: on one hand, the halloysite nanotube has a nano hollow tubular structure and a larger specific surface area, so the halloysite nanotube has stronger adsorption capacity and can play a good slow release role as a carrier of the antibacterial agent such as nano Ag and the like; on the other hand, research has shown that HNTs/polymer composites tend to have higher mechanical strength, better processability and thermal stability. The halloysite nanotube is added into the polymer, and the mechanical property and the thermodynamic property of the PLA/starch foaming material can be improved by utilizing the dispersion or interface effect and the like of the halloysite nanotube.

Patent CN101385478B discloses a method for preparing a chilled meat preservative film pad, which comprises preparing a natural preservative into a solution, spraying the solution on absorbent paper, drying, shaping, filling a punctured polyethylene film, and sealing to obtain the preservative film pad. The preparation method is simple in process and easy to operate, but the freshness retaining durability is poor, the preservative is not favorable for long-acting and stable action when being added into the absorbent paper, and the raw materials utilized by the method are not degradable, so that the problem of white pollution is aggravated if the preservative is produced in large quantities and put into the market.

Patent CN101156620A discloses a food fresh-keeping pad which can release carbon dioxide and chlorine dioxide gas with various functions of fresh-keeping, preservation, deodorization, etc., and also comprises a liquid absorption material for absorbing liquid exuded from meat, so as to achieve the bacteriostatic and preservative effects. But the gas can be quickly diffused into the air after being released, the action time is short, the bacteriostatic atmosphere is difficult to form around the food, and the fresh-keeping effect has certain limitation.

Patent CN101935440A discloses a preparation method of a starch/polylactic acid blending antibacterial active packaging material with antibacterial active controlled release function, which controls the dispersion phase of an antibacterial agent and a compatilizer by controlling the proportion of various raw materials and the feeding sequence, thereby realizing the control release of the antibacterial agent and the improvement of the mechanical property of the material; however, the added natural antibacterial agent has poor heat resistance, and although the antibacterial agent can be controlled to be released, the antibacterial activity of the antibacterial agent is partially lost under the high-temperature condition, the antibacterial effect is reduced, and the antibacterial agent cannot be used for a long time.

Patent CN101983568 discloses a halloysite silver-carrying antibacterial agent and a preparation method thereof, wherein halloysite is activated and dried at first, then added into silver nitrate solution for reaction, and stirred, filtered and dried to obtain the halloysite silver-carrying antibacterial agent which has good antibacterial effect, broad-spectrum antibacterial property, certain slow release property and good heat resistance. However, only a small amount of silver can be loaded on HNTs by means of direct water bath heating and stirring, and the loading rate of the method is low.

Patent CN109627558A discloses an antifog preservative film, wherein urea activated nano halloysite loaded 3-propyl-2-enoyloxypropane-1-sodium sulfonate is added into raw materials, hydrogen peroxide is used for pretreating nano halloysite, then the nano halloysite is calcined in a resistance furnace and mixed and stirred with urea solution, impregnation liquid dissolved with 3-propyl-2-enoyloxypropane-1-sodium sulfonate is added into a reaction kettle for reaction, and a nano halloysite compound is obtained through suction filtration and drying. The method has the disadvantages of complicated preparation process, harsh experimental conditions and difficulty in realizing large-scale production.

Patent CN109486211A discloses a casein-based packaging film, a preparation method thereof and application thereof in preserved meat preservation, wherein casein is used as a film forming substrate, and halloysite nanotubes, a cross-linking agent, a plasticizer and a preservative are added for film coating and forming to obtain the casein-based packaging film. The halloysite nanotubes in the invention are used as a reinforcing material of a packaging film, the physical properties of the film are enhanced, and the function of loading an antibacterial agent is not involved.

Disclosure of Invention

The invention provides a degradable food fresh-keeping pad with the functions of bacteriostasis, shock resistance and moisture absorption and a preparation method thereof. The freshness-retaining pad provided by the invention has the internal and external dual antibacterial effects, takes account of both the timeliness and the long-acting property of the antibacterial property, has broad-spectrum antibacterial capability and also has certain water absorption and shock resistance, and ensures the product quality.

The invention is realized by the following technical scheme:

a method for preparing a degradable food fresh-keeping pad with antibacterial, shockproof and moisture absorption effects comprises spraying a natural antibacterial agent on the surface of an antibacterial PLA/starch foaming material, and coating the antibacterial PLA/starch foaming material with a perforated polylactic acid film.

The antibacterial PLA/starch foaming material comprises the following raw materials in parts by weight: 75-85 parts of PLA, 15-25 parts of starch, 1-3 parts of HNTs-antibacterial agent composite material, 0.5-2 parts of foaming agent and 2-5 parts of compatibilizer.

The preparation method of the antibacterial PLA/starch foaming material comprises the following steps:

(1) respectively drying PLA granules and starch, cooling and uniformly mixing to obtain mixed granules;

(2) mixing the foaming agent, the HNTs-antibacterial agent composite material and the compatibilizer, adding the mixture into the mixed particles, and uniformly stirring to obtain a mixed material;

(3) and adding the mixed material into a double-screw extruder, extruding and foaming, and cooling and shaping to obtain the antibacterial PLA/starch foaming material.

The HNTs-antibacterial agent composite material takes Halloysite Nanotubes (HNTs) as carriers of antibacterial agents, the antibacterial agents comprise nano-particle antibacterial agents and/or organic antibacterial agents, and the nano-particle antibacterial agents comprise nano-Ag and nano-TiO₂Nano, nanoZnO, nano MgO and nano CaCO₃The organic antibacterial agent comprises one or more of gallic acid, sorbic acid, citral, p-anisic aldehyde and cinnamaldehyde. The HNTs can respectively load the antibacterial agents, the freshness protection pad added with different antibacterial agents can be applied to different types of food packages, and the multiple antibacterial agents are mixed for use to achieve the synergistic antibacterial effect.

When the antibacterial agent is a nano-particle antibacterial agent, the preparation method of the HNTs-antibacterial agent composite material comprises the following steps: dispersing HNTs powder in deionized water according to the mass ratio of 1 (95-105) to obtain a suspension, then ultrasonically dispersing the suspension at 55-65 ℃ for 2h, and adding the mixture according to the mass ratio (0.8-1.2) to the HNTs: 1, stirring in a magnetic water bath for 2-3 hours at the water bath temperature of 60-70 ℃, then compounding the nano-particle antibacterial agent and the water bath by ultrasonic oscillation, performing vacuum filtration to obtain a compound, and washing and drying to obtain the HTNs-composite antibacterial agent taking the nano-particle antibacterial agent as an antibacterial active substance.

When the antibacterial agent is an organic antibacterial agent, the preparation method of the HNTs-antibacterial agent composite material comprises the following steps: mixing the organic antibacterial agent according to the ratio of 1: (95-105) dissolving the mixture in an organic solvent, and adding the mixture in an amount which is 1: (0.8-1.2) magnetically stirring the HNTs powder at 55-65 ℃ for 2-3 h or ultrasonically stirring the HNTs powder at 55-65 ℃ for 2-3 h to promote the organic antibacterial agent and the HNTs to form a compound, then carrying out vacuum filtration on the suspension, washing and drying to obtain the HTNs-composite antibacterial agent taking the organic antibacterial agent as an antibacterial active substance.

The organic solvent is preferably absolute ethanol.

In the step (1), the drying condition is drying at 55-75 ℃ for 4-8h, preferably drying at 60-70 ℃ for 3-6 h.

The processing temperatures of the 1-7 areas of the double-screw extruder in the step (3) are respectively 140-150 ℃, 150-160 ℃, 155-165 ℃, 170-180 ℃, 160-170 ℃, 145-155 ℃, preferably 145 ℃, 155 ℃, 160 ℃, 175 ℃, 175 ℃, 165 ℃ and 150 ℃, and the rotating speed of the double screws is 180-300 r/min, preferably 200-250 r/min.

Preferably, the compatibilizer is prepared from a plasticizer, a chain extender, a crosslinking agent 1: 1:1, mixing and forming.

Preferably, the blowing agent is azodicarbonamide (AC blowing agent).

Preferably, the plasticizer is acetyl butyl citrate (ATBC), the chain extender is Glycidyl Methacrylate (GMA), and the cross-linking agent is Citric Acid (CA) and/or Maleic Anhydride (MAH).

Preferably, the natural antibacterial agent is one or more of plant essential oil, chitosan, carvacrol, tea polyphenol, rosemary extract, potassium sorbate and lactic acid bacteria streptococcus, and the plant essential oil comprises one or more of thyme essential oil, cinnamon essential oil and clove essential oil, and has a remarkable antibacterial effect.

Further preferably, the amount of the natural antibacterial agent sprayed on the antibacterial PLA/starch foaming material is 1-3% of the mass of the antibacterial PLA/starch foaming material, and the natural antibacterial agent is prepared into a solution and then sprayed on the surface of the antibacterial PLA/starch foaming material.

Preferably, the preparation method of the perforated polylactic acid film comprises the following steps: preparing a PLA film by casting PLA particles through a single-screw casting machine, and punching holes on the film by using a punching machine, wherein the diameter of each punching hole is 0.3-0.5 mm, and the density of each punching hole is 6-8 holes/cm²。

A degradable food fresh-keeping pad with antibacterial, shockproof and moisture absorption effects is prepared by any one of the above methods.

The antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad prepared by the method is applied to the transportation and sale links of foods such as cold fresh meat, seafood and the like, can inhibit the growth and propagation of microorganisms, adsorb exuded juice and ensure the product quality; the fruit and vegetable transportation method is also applied to the transportation link of the fruits and vegetables, so that the spoilage of the fruits and vegetables is reduced, the damage of the fruits and vegetables caused by transportation bump is relieved, and the waste is reduced; the product can be used for household use by consumers, is suitable for storing fresh food purchased at home, can ensure the freshness of the food, reduces the invasion of microorganisms, and has wide application prospect and important social and economic benefits.

Compared with the prior art, the invention has the following advantages and innovations:

(1) in the aspect of foaming materials, the foaming process is improved. The foaming system is added with a mixture of a plasticizer, a chain extender and a cross-linking agent 1: 1:1 proportion of compatibilizer, which increases the interface compatibility of PLA/starch system and improves the mechanical property and heat resistance of the foaming material;

(2) in the HNTs-antibacterial agent composite material, the halloysite nanotube is used as a carrier of the antibacterial agent, and the application of the antibacterial packaging material is pioneering, and no relevant report is found at home and abroad. The addition of the HTNs-compound antibacterial agent has the following advantages: firstly, the halloysite nanotube is used as a carrier of an antibacterial agent, and has a slow release regulation effect on the release of the antibacterial agent, so that the antibacterial effect can be realized for a long time, and the fresh-keeping effect is obvious; secondly, the halloysite nanotubes are added into the film-forming base material, so that the mechanical property and the thermodynamic property of the PLA/starch foaming material can be improved, and the practicability and the durability of the fresh-keeping pad are enhanced; thirdly, the halloysite nanotube has good dispersibility in polymers and is not easy to agglomerate due to the special surface structure and the charge property of the halloysite nanotube; fourthly, the halloysite nanotubes are respectively loaded with different antibacterial agents and are added into the foaming base material together, so that the synergistic antibacterial effect is achieved;

(3) the inorganic antibacterial agent and the natural antibacterial agent are used in a dual mode, so that the antibacterial effect is enhanced, the complementary effect of the antibacterial spectrum of the foaming material can be achieved by selecting the proper natural antibacterial agent, and the freshness protection pad has a wider antibacterial capability. The inner halloysite nanotube loaded antibacterial agent is slowly released, the outer natural antibacterial agent quickly plays a role by volatilization or contact with food, and the timeliness and the long-acting property of the antibacterial are both considered.

(4) The fresh-keeping pad prepared by the invention has a certain juice adsorption effect, and bacteria are easy to breed in liquid exuded by meat, so that the meat is deteriorated and rotten. The foamed starch/PLA substrate still has certain water absorption, and the absorption of the liquid can obviously inhibit the growth of bacteria.

(5) The fresh-keeping pad prepared by the invention also has the functions of shock resistance and moisture absorption. Because the starch has expansibility during extrusion, after the high-temperature starch melt and the PLA are extruded, the pressure in the materials is released to form a porous structure, and the shockproof function is realized; the starch has good water absorption, can be combined with water molecules through intramolecular hydrogen bonds after foaming, so as to adsorb juice exuded from meat, water vapor generated by respiration of fruits and vegetables, and the like, and has a moisture absorption function.

Drawings

FIG. 1 is a schematic view of the overall structure of the bacteriostatic, shockproof and moisture-absorbing degradable food preservation pad of the invention;

FIG. 2 is a schematic representation of HNTs-antimicrobial composite wherein 1-halloysite nanotubes, 2-antimicrobial;

wherein, the film comprises 1-perforated polylactic acid film, 2-antibacterial PLA/starch foaming material, 3-HNTs-antibacterial agent composite material, 4-halloysite nanotube, 5-antibacterial agent and 6-perforated holes of the polylactic acid film.

Detailed Description

In order to better explain the invention, the following is used to further clarify the main content of the invention in connection with specific examples, but the invention is not limited to the following examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.