CN113045786A - Multifunctional self-fit film and method and application for quickly positioning and forming film - Google Patents
Multifunctional self-fit film and method and application for quickly positioning and forming film Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a multifunctional self-fit film, a method for quickly positioning and forming films on the surfaces of different substrates and application thereof. The invention takes natural polymer/modified natural polymer and natural cross-linking agent as raw materials, adjusts the performance of the film by adding functional active ingredients, and obtains a stable three-dimensional network structure to coat the surface of a matrix by quickly cross-linking and molding the cross-linking agent and the natural polymer on the surface of the matrix, and the self-fitting film can be quickly positioned on the surfaces of different matrixes to form the self-fitting film, thereby realizing the synchronous operation and completion of the preparation and packaging processes of the self-fitting film. The self-bonding film prepared by the invention has high film forming speed and strong toughness, and can effectively overcome the problems of brittleness and difficult heat sealing and packaging of the existing natural polymer film; the self-adaptation film is high in universality, wide in raw material source, green and degradable, adjustable in function, capable of meeting requirements of different application scenes, and capable of being applied to preservation of fruits, vegetables, meat and other foods and protection of public health safety.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a multifunctional self-fit film, a method for quickly positioning and forming the film on the surfaces of different substrates and application of the multifunctional self-fit film in food preservation or public health safety protection and the like.
Background
In recent years, due to the increasing environmental protection problem caused by non-degradable materials, researches on replacing non-degradable petroleum-based products with degradable natural polymers are receiving more and more attention. The natural polymer raw materials have wide sources and low price, can be regenerated and are ideal raw materials. However, products such as films prepared by processing natural polymers are generally brittle and very fragile, and are non-thermoplastic materials, which cannot be packaged by means of thermal processing, and in addition, the common packaging method is difficult to adhere to the substrate, which causes gaps and has poor packaging effect, so that the utilization of natural polymers still presents a great challenge at present.
The novel degradable composite material can be prepared by using a mode of blending natural polymers and traditional petroleum-based polymers, but the material is only a natural polymer part which is degraded, and the petroleum-based polymer part still can bring the problem of environmental pollution. In addition, the coating is also one of the application modes of the natural polymer materials, and the protective film is formed by preparing a coating solution for coating, so that the problem that the natural polymer is difficult to heat seal is solved, but after the solvent of the natural polymer solution is volatilized, the natural polymer solution usually shrinks and agglomerates due to strong intermolecular interaction, and particularly on some smooth and hydrophobic surfaces, the uniform coating is difficult to obtain by a dip coating or spray coating mode. Therefore, how to form natural polymer films on the surfaces of substrates with different properties in a simple and convenient manner still has a challenge. Meanwhile, the performance regulation of the natural polymer membrane is also of great importance, and with the development of the society, membranes with special functions, such as antibiosis, antioxidation, antivirus, quality monitoring and the like, are required, so that the regulation of the performance of the natural polymer membrane has very important significance. At present, no report is found about the preparation of multifunctional self-bonding film on the surface of a substrate by utilizing natural macromolecules.
Disclosure of Invention
The invention aims to overcome the problems of brittleness, difficult heat-sealing packaging and the like of the existing natural polymer film, and provides a multifunctional self-conforming film, a method for quickly positioning and forming the film on the surfaces of different substrates and application thereof. The invention takes natural polymer/modified natural polymer and natural cross-linking agent as raw materials, adjusts the performance of the film by adding functional active ingredients, and can quickly position and form self-fitting films on the surfaces of different matrixes by the characteristic that the cross-linking agent and the natural polymer are quickly cross-linked and formed on the surfaces of the matrixes, thereby realizing the synchronous operation and completion of the preparation and packaging processes of the self-fitting films. The self-fitting film has adjustable functions, and can be applied to food preservation of fruits, vegetables, meat and the like or public health safety protection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a multifunctional self-conforming membrane is prepared from natural polymers/modified natural polymers, a natural cross-linking agent and functional active ingredients, wherein the weight ratio of the raw materials is as follows: the natural polymer/modified natural polymer comprises a natural cross-linking agent and functional active ingredients, wherein the functional active ingredients are = 2-10: 3-15: 0.01-0.15;
the natural polymer/modified natural polymer is selected from one or more of starch and its derivatives, chitin/chitosan and its derivatives, cellulose and its derivatives, lignin and its derivatives, alginate and alginate ester, gelatin, pectin, mussel mucin, zein and wheat protein;
the natural cross-linking agent is selected from one or more of tannic acid, citric acid, ascorbic acid, hyaluronic acid, humic acid, vanillin, genipin and tea polyphenol;
the functional active ingredients are selected from one or more of tannic acid, dimethyl fumarate, ethephon, sodium chlorite, curcumin, salicylic acid, anthocyanin, tea polyphenol, fendorin, chlorine dioxide, oregano oil, tea tree oil, cinnamaldehyde, chloramine T and lysozyme.
Further, in the multifunctional self-mating film, the starch derivative is cationic starch, carboxymethyl starch or esterified starch; the chitosan derivative is hydroxypropyl chitosan, carboxymethyl chitosan or beta-cyclodextrin grafted chitosan.
In the multifunctional self-mating film, the cellulose derivative is hydroxyethyl cellulose, carboxymethyl cellulose or hydroxypropyl methyl cellulose; the lignin derivative is lignosulfonate or a lignin graft copolymer.
The method for quickly positioning and forming the multifunctional self-fitting film comprises the following steps:
(1) according to the weight ratio of the raw material components, taking natural polymer/modified natural polymer, natural cross-linking agent and functional active component for standby, then adding water into the natural polymer/modified natural polymer to prepare a solution with the mass concentration w/w of 2-8%, and adding water (or other solvents) into the natural cross-linking agent to prepare a solution with the mass concentration w/w of 3-10%;
(2) adding corresponding functional active ingredients into a natural polymer/modified natural polymer solution as required, stirring, performing functional regulation, uniformly distributing the solution on the surface of a specified substrate in a dip-coating or spraying manner, coating a layer of the solution on the surface of the substrate, rapidly coating a layer of natural cross-linking agent solution on the surface in a dip-coating or spraying manner, rapidly cross-linking the two solutions at normal temperature (within 10-20 s) to form a stable three-dimensional network structure, and volatilizing the solvent to obtain a film which is self-fitted with the surface of the substrate on the surface of the specified substrate.
Some of the materials used in the present invention can be used as both natural cross-linking agents and functional active ingredients. In the method for quickly positioning and forming the film of the multifunctional self-conforming film, when the natural cross-linking agent and the functional active ingredient adopted for preparing the self-conforming film are the same substance, the functional active ingredient is not required to be added into the natural polymer/modified natural polymer solution for functional regulation and control, and the natural cross-linking agent is directly added with water to prepare a solution with the mass concentration w/w of 3-10% for use.
The function of the multifunctional self-conforming film prepared by the invention can be regulated, and the prepared self-conforming film has the effects of antibiosis, fresh keeping, sanitation protection and the like, and can be applied to food fresh keeping or public health safety protection.
The invention has the advantages or innovation points that: (1) the self-conforming film of the matrix can be rapidly prepared and coated by in-situ rapid crosslinking molding of the natural polymer/modified natural polymer and the natural crosslinking agent, and the obtained self-conforming film has the advantages of a thin film and a coating and integrates molding processing and film use. (2) The regulation and control of the self-conforming membrane performance can be realized by simply adjusting the raw material components, so that the self-conforming membrane meeting different application requirements is obtained, and multifunctional customization can be realized. (3) The method has the advantages of convenience, flexibility, low cost, low energy consumption, stable product positioning and film forming according to needs, simplified use flow and the like.
The invention has the beneficial effects that:
1. the invention takes natural polymer/modified natural polymer and natural cross-linking agent as raw materials, adjusts the performance of the film by adding functional active ingredients, obtains a stable three-dimensional network structure to coat the surface of the matrix by quickly cross-linking and molding the cross-linking agent and the natural polymer on the surface of the matrix (only 10-20 s), can quickly position on the surfaces of different matrixes to form self-matching films, and realizes the synchronous operation and completion of the preparation and packaging processes of the self-matching films. The self-bonding film prepared by the invention has high film forming speed and strong toughness, and can effectively overcome the problems of brittleness and difficult heat sealing and packaging of the existing natural polymer film.
2. The function of the self-conforming membrane prepared by the invention can be regulated, and the multi-function customization of the self-conforming membrane can be realized by changing the types of natural polymers/modified natural polymers or cross-linking agents and adding partial functional active ingredients. If the antibacterial and antiviral components are added, the self-conforming film can be endowed with the characteristics of sterilization and disinfection, so that the self-conforming film with antibacterial, fresh-keeping and sanitary protection effects can be obtained, and the self-conforming film can be applied to food fresh keeping of fruits, vegetables, meat and the like and public health safety protection, including but not limited to handles, escalators, elevator buttons and the like in public areas. The addition of components with environmental stimulus response (such as PH, enzyme, bacteria and the like) can endow the self-adaptive membrane with the property of stimulus response, and obtain the intelligent self-adaptive membrane with the functions of quality monitoring and the like. The technology has very important practical value for solving the problems of poor self-antibacterial effect, narrow application range and the like of the natural polymer film, realizes the regulation and control of self-conforming film performance by simply regulating and controlling the composition of the natural polymer film, and designs and prepares the self-conforming film with different functions and meeting the requirements of different application scenes.
3. The self-bonding film prepared by adding functional active ingredients (such as tea polyphenol, oregano oil, cinnamyl aldehyde and the like) with antibacterial and antiviral effects has the effects of resisting bacteria, keeping fresh and the like, can be used for keeping food such as fruits, vegetables and meat, can be used for quickly positioning the surface of the food to form the self-bonding film visible to the naked eye when in use, and then keeps the food fresh at normal temperature or low temperature, has good fresh-keeping effect, is safe and nontoxic, and can effectively slow down the rotting speed of the food.
4. By adopting the technical scheme of the invention, the self-fit film with the disinfection and antibacterial effects can be positioned at the designated position, and a new method is provided for public health safety protection.
5. The method has the advantages of simple process route, low requirement on equipment, high universality, wide raw material source, greenness and degradability, and conforms to the national environmental protection development concept.
Drawings
FIG. 1 is a surface diagram of a fruit obtained by performing a self-matching film-coating and film-forming process on a fruit with different smooth and concave-convex surfaces by using a method for rapidly positioning and forming a film by using a self-matching film in embodiment 1 of the present invention;
fig. 2 is a surface diagram of a dragon fruit obtained by performing a positioning film-forming process on a local surface of the dragon fruit by using a rapid positioning film-forming method of a local positioning type self-matching film in embodiment 2 of the present invention;
fig. 3 is a surface diagram of a self-mating film formed at a designated position of a wooden material, a ceramic material, and a stainless steel material by a method for rapidly positioning a self-mating film in embodiment 3 of the present invention, where in fig. 3, the designated position surfaces of the wooden material and the ceramic material are surface condition diagrams just after spraying a natural cross-linking agent solution, and the designated position surface of the stainless steel material is a surface diagram after drying in the air to form the self-mating film;
fig. 4 is a comparison graph of the state of the litchi and syzygium jambos fruits subjected to the self-fitting film integral coating film forming treatment by adopting the method for quickly positioning and forming the film of the self-fitting film in the embodiment 1 of the invention and the states of the litchi and the syzygium after being placed for a period of time, as can be seen from fig. 4, the litchi surfaces in the blank control group begin to go moldy, the syzygium is obviously deteriorated and blackened, the moldy phenomenon does not occur on the litchi surfaces in the self-fitting film group, the syzygium still keeps the original color and is not deteriorated, and the litchi and the syzygium in the self-fitting film group are obviously fresher;
fig. 5 is a comparison graph of the surface of the part of the dragon fruit which is not subjected to the self-matching film forming treatment (i.e. blank control) in the same dragon fruit and the surface of the part of the dragon fruit which is subjected to the self-matching film forming treatment after the dragon fruit which is subjected to the local positioning type self-matching film forming treatment by using the method for quickly positioning and forming the film on the surface of the part of the dragon fruit in embodiment 2 of the invention is placed for a period of time, as can be seen from fig. 4, the surface of the hollow part of the dragon fruit in the same dragon fruit is seriously rotted and mildewed, while the surface of the dragon fruit with the self-matching film part is only slightly rotted;
as can be seen from figures 4 and 5, the self-conforming film of the present invention has a good fresh-keeping effect on fruits, and can effectively slow down the rotting speed of foods.
Detailed Description
The technical solution of the present invention is further specifically described below by way of examples.
Example 1
The method for quickly positioning and forming the film of the integrally coated self-fitting film comprises the following steps:
(1) the natural polymer/modified natural polymer is carboxymethyl cellulose and chitosan, and the natural cross-linking agent and the functional active component are tannic acid; mixing carboxymethyl cellulose, chitosan, a natural cross-linking agent and functional active ingredients with the weight ratio of 1:1:4.9:0.1 according to the weight ratio of the raw materials, taking the carboxymethyl cellulose, the chitosan and tannic acid for later use, mixing the carboxymethyl cellulose and the chitosan, adding water to prepare a solution with the mass concentration w/w of 2%, and adding water to the tannic acid to prepare a solution with the mass concentration w/w of 5%;
(2) the method comprises the steps of dip-coating a layer of carboxymethyl cellulose and chitosan solution on the surface of a whole substrate in a dip-coating manner to coat the surface of the substrate with a layer of the solution, then soaking the substrate in a tannic acid solution, quickly coating a layer of the tannic acid solution on the surface in a dip-coating manner, taking up the substrate, quickly crosslinking the two solutions at normal temperature (within 10-20 s) to form a stable three-dimensional network structure to form a gel film, and naturally airing the gel film to obtain an integrally-coated self-bonding film on the surface of the substrate (the fruit surface image obtained after the fruit with different surfaces, namely smooth and concave-convex surfaces, is subjected to integral coating film-forming treatment by the self-bonding film is shown in figure 1).
Example 2
The method for quickly positioning and forming the film by the local positioning type self-fitting film comprises the following steps:
(1) the natural polymer/modified natural polymer is carboxymethyl cellulose and chitosan, and the natural cross-linking agent and the functional active component are tannic acid; mixing carboxymethyl cellulose, chitosan, a natural cross-linking agent and functional active ingredients with the weight ratio of 1:1:4.9:0.1 according to the weight ratio of the raw materials, taking the carboxymethyl cellulose, the chitosan and tannic acid for later use, mixing the carboxymethyl cellulose and the chitosan, adding water to prepare a solution with the mass concentration w/w of 2%, and adding water to the tannic acid to prepare a solution with the mass concentration w/w of 5%;
(2) coating a carboxymethyl cellulose and chitosan solution on the surface of a specified base body part in a spraying manner to coat a layer of the solution on the specified part, then quickly coating a layer of tannic acid solution on the specified part in a spraying manner, quickly crosslinking the two solutions at normal temperature (within 10-20 s) to form a gel film, and naturally drying the gel film to obtain a self-bonding film on the surface of the specified base body part (the surface of the dragon fruit obtained after the local surface of the dragon fruit is subjected to positioning film-forming treatment is shown in figure 2).
Example 3
In the aspect of public health protection:
the method for quickly positioning and forming the self-fitting film comprises the following steps:
(1) the natural polymer/modified natural polymer is carboxymethyl chitosan, the natural cross-linking agent is tannic acid and ascorbic acid, and the functional active ingredient is sodium chlorite; according to the weight ratio of carboxymethyl chitosan to tannic acid to ascorbic acid to sodium chlorite =2.5:3:0.2:0.15, carboxymethyl chitosan, tannic acid, ascorbic acid and sodium chlorite are taken for standby, water is added into the carboxymethyl chitosan to prepare a solution with the mass concentration w/w of 2.5%, the tannic acid and the ascorbic acid are mixed and then added with the water to prepare a solution of tannic acid (w/w, 3%) + ascorbic acid (w/w, 0.2%);
(2) adding sodium chlorite into carboxymethyl chitosan solution, stirring, dissolving, functional regulation and control, spraying the solution onto the surface of the appointed position, coating one layer of the solution onto the appointed position, and spraying one layer of tannic acid and ascorbic acid solution onto the corresponding position. (the surface map of the rapid positioning film-forming treatment of the self-fit film at the designated positions of the wood material, the ceramic material and the stainless steel material by adopting the method is shown in fig. 3. in fig. 3, the designated position surfaces of the wood material and the ceramic material are the surface condition maps just after the natural cross-linking agent solution is sprayed, and the designated position surfaces of the stainless steel material are the surface maps after the self-fit film is formed by airing).
Example 4
A method for quickly positioning and forming a self-matching film for fruit and vegetable preservation comprises the following steps:
(1) the natural polymer/modified natural polymer is carboxymethyl starch and hydroxypropyl chitosan, the natural cross-linking agent is citric acid, and the functional active component is tea polyphenol; according to the weight ratio of carboxymethyl starch, hydroxypropyl chitosan, citric acid and tea polyphenol =2:3:8:0.08, taking carboxymethyl starch, hydroxypropyl chitosan, citric acid and tea polyphenol for standby, then mixing carboxymethyl starch and hydroxypropyl chitosan, adding water to prepare a solution with the mass concentration w/w of 5%, and adding water to citric acid to prepare a solution with the mass concentration w/w of 8%;
(2) adding tea polyphenol into a solution of carboxymethyl starch and hydroxypropyl chitosan, stirring, dissolving, performing functional regulation, uniformly distributing the solution on the surface of a specified substrate in a dip-coating or spraying manner, coating a layer of the solution on the surface of the substrate, rapidly coating a layer of citric acid solution on the surface in a dip-coating or spraying manner, rapidly crosslinking the two solutions at normal temperature to form a stable three-dimensional network structure, and volatilizing the solvent to obtain a film which is self-matched with the surface of the substrate on the surface of the specified substrate.
Example 5
A method for quickly positioning and forming a self-fitting film for meat food preservation comprises the following steps:
(1) the natural polymer/modified natural polymer is hydroxypropyl methylcellulose and pectin, the natural cross-linking agent is vanillin, and the functional active component is cinnamaldehyde; taking hydroxypropyl methyl cellulose, pectin, vanillin and cinnamaldehyde for later use according to the weight ratio of hydroxypropyl methyl cellulose to pectin to vanillin to cinnamaldehyde =5:2:10:0.1, mixing the hydroxypropyl methyl cellulose and the pectin, adding water to prepare a solution with the mass concentration w/w of 7%, and adding water to the vanillin to prepare a solution with the mass concentration w/w of 10%;
(2) adding cinnamic aldehyde into a solution of hydroxypropyl methyl cellulose and pectin, mixing and stirring, performing functional regulation, uniformly distributing the solution on the surface of the appointed meat product in a dip-coating or spraying manner, coating a layer of the solution on the surface, rapidly coating a layer of vanillin solution on the surface in a dip-coating or spraying manner, rapidly crosslinking the two solutions at normal temperature to form a stable three-dimensional network structure, and volatilizing the solvent to obtain a film which is self-matched with the surface of the matrix on the surface of the appointed meat product.
Example 6
A method for rapid positioning film formation of a self-conforming film for a stair railing, comprising the steps of:
(1) the natural polymer/modified natural polymer is hydroxypropyl methylcellulose and chitosan, the natural cross-linking agent is tannic acid, and the functional active ingredient is dimethyl fumarate; taking hydroxypropyl methyl cellulose, chitosan, tannic acid and dimethyl fumarate for later use according to the weight ratio of hydroxypropyl methyl cellulose, chitosan, tannic acid and dimethyl fumarate =5:5:15:0.10, mixing the hydroxypropyl methyl cellulose and the chitosan, adding water to prepare a solution with the mass concentration w/w of 8%, and adding water to the tannic acid to prepare a solution with the mass concentration w/w of 10%;
(2) adding dimethyl fumarate into a solution of hydroxypropyl methylcellulose and chitosan, stirring, dissolving, performing functional regulation, uniformly distributing the solution on the surface of a designated stair railing in a spraying manner, coating a layer of the solution on the surface of the stair railing, quickly coating a layer of tannic acid solution on the surface in a spraying manner, quickly crosslinking the two solutions at normal temperature to form a stable three-dimensional network structure, and volatilizing the solvent to obtain a film which is self-fitted with the surface of the stair railing on the surface of the designated stair railing.
Example 7
A method for quickly positioning and forming a multifunctional self-conforming film comprises the following steps:
(1) the natural polymer/modified natural polymer is selected from sodium alginate and sodium lignosulfonate, the natural cross-linking agent is selected from citric acid, and the functional active ingredient is tea tree oil; according to the weight ratio of sodium alginate to sodium lignosulfonate to citric acid to tea tree oil =3:1:6:0.02, taking sodium alginate, sodium lignosulfonate, citric acid and tea tree oil for later use, mixing the sodium alginate and the sodium lignosulfonate, adding water to prepare a solution with the mass concentration w/w of 4%, and adding water to the citric acid to prepare a solution with the mass concentration w/w of 6%;
(2) adding tea tree oil into a solution of sodium alginate and sodium lignosulphonate, stirring, mixing, performing functional regulation, uniformly distributing the solution on the surface of a specified matrix in a dip-coating or spraying manner, coating a layer of the solution on the surface of the matrix, quickly coating a layer of citric acid solution on the surface in a dip-coating or spraying manner, quickly crosslinking the two solutions at normal temperature (within 10-20 s) to form a stable three-dimensional network structure, and volatilizing the solvent to obtain a film which is self-matched with the surface of the matrix on the surface of the specified matrix.
Claims (6)
1. The multifunctional self-conforming membrane is characterized by being prepared from natural polymers/modified natural polymers, a natural cross-linking agent and functional active ingredients, wherein the weight ratio of the raw materials is as follows: the natural polymer/modified natural polymer comprises a natural cross-linking agent and functional active ingredients, wherein the functional active ingredients are = 2-10: 3-15: 0.01-0.15;
the natural polymer/modified natural polymer is selected from one or more of starch and derivatives thereof, chitin/chitosan and derivatives thereof, cellulose and derivatives thereof, lignin and derivatives thereof, alginate and alginate ester, gelatin, pectin, mussel mucin, zein and wheat protein;
the natural cross-linking agent is selected from one or more of tannic acid, citric acid, ascorbic acid, hyaluronic acid, humic acid, vanillin, genipin and tea polyphenol;
the functional active ingredients are selected from one or more of tannic acid, dimethyl fumarate, ethephon, sodium chlorite, curcumin, salicylic acid, anthocyanin, tea polyphenol, fendorin, chlorine dioxide, oregano oil, tea tree oil, cinnamaldehyde, chloramine T and lysozyme.
2. The multifunctional self-conforming film according to claim 1 wherein said starch derivative is a cationic starch, a carboxymethyl starch or an esterified starch; the chitosan derivative is hydroxypropyl chitosan, carboxymethyl chitosan or beta-cyclodextrin grafted chitosan.
3. The multifunctional self-mating film according to claim 1, wherein the cellulose derivative is hydroxyethyl cellulose, carboxymethyl cellulose or hydroxypropyl methyl cellulose; the lignin derivative is lignosulfonate or a lignin graft copolymer.
4. A method for rapid positional film formation of a multifunctional self-conforming film according to any one of claims 1 to 3 comprising the steps of:
(1) according to the weight ratio of the raw material components, taking natural polymer/modified natural polymer, natural cross-linking agent and functional active component for standby, then adding water into the natural polymer/modified natural polymer to prepare a solution with the mass concentration w/w of 2-8%, and adding water into the natural cross-linking agent to prepare a solution with the mass concentration w/w of 3-10%;
(2) adding corresponding functional active ingredients into a natural polymer/modified natural polymer solution as required, stirring, performing functional regulation, uniformly distributing the solution on the surface of a specified substrate in a dip-coating or spraying manner, coating a layer of the solution on the surface of the substrate, rapidly coating a layer of natural cross-linking agent solution on the surface in a dip-coating or spraying manner, rapidly cross-linking the two solutions at normal temperature to form a stable three-dimensional network structure, and volatilizing the solvent to obtain a film which is self-matched with the surface of the substrate on the surface of the specified substrate.
5. The method for rapidly positioning and forming the multifunctional self-conforming membrane according to claim 4, wherein when the natural cross-linking agent and the functional active ingredient adopted for preparing the self-conforming membrane are the same substance, the functional active ingredient is not added into the natural polymer/modified natural polymer solution for functional regulation, and the natural cross-linking agent is directly added with water to prepare a solution with the mass concentration w/w of 3-10% for use.
6. The use of the multifunctional self-conforming film of claim 1 in food preservation or public health safety protection.
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