CN115260635A - Waterproof breathable antibacterial DDS plastic film and processing technology thereof - Google Patents
Waterproof breathable antibacterial DDS plastic film and processing technology thereof Download PDFInfo
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Abstract
The invention provides a waterproof breathable antibacterial DDS plastic film which comprises a resin material and a DDS medicament carrier arranged in the resin material; the DDS medicament carrier is prepared by deep processing of nano porous diatom minerals; the deep processing steps of the nano porous diatom mineral comprise: purifying, repairing holes, modifying and filling the medicine; the hole repairing of the nano porous diatom mineral is hole expanding or hole shrinking; the modification of the nanoporous diatom mineral comprises a hydrophobic modification; the nano porous diatom mineral is filled with a filling agent; the design realizes high air permeability, simple preparation process and low cost, and compared with the traditional low-waterproof, low-air-permeability, non-environment-friendly and artificially-synthesized film, the film has low cost and environmental protection, and is a natural environment-friendly, high-air-permeability, high-waterproof and high-antibacterial plastic film.
Description
Technical Field
The invention relates to the field of preservative films, in particular to a waterproof breathable antibacterial DDS plastic film.
Background
When vegetables and fruits are in the packaging bag, the vegetables and fruits can breathe and emit ethylene in the continuous maturation process, the breathing and the ethylene generation quantity can be obviously increased, the color, the taste, the smell and the texture of the vegetables and fruits can be rapidly and obviously changed, and a plurality of bacteria and fungi can also generate ethylene in the packaging bag. The packaging bag can keep 1-5% of oxygen, 2-10% of carbon dioxide and less than 1ppm of ethylene, so that the vegetables and fruits can be kept fresh, and the waterproof function of the packaging bag is particularly important.
The waterproof breathable film is a preservative film which can not be penetrated by water under certain pressure in the using process, and gases emitted by vegetables and fruits, particularly carbon dioxide, ethylene, amine gas and the like, can penetrate through the preservative film to be discharged, and oxygen can enter.
At present, the existing waterproof breathable preservative films in the market are mainly polymer crystalline films, nanometer plant fiber films, zeolite Zeolite films, chitin Chitosan films and the like, and the synthetic films have low air permeability, complex relative preparation process and high cost, and have the problems of environmental protection and toxin residue caused by toxic chemicals used in the refining process, and the application range of the waterproof breathable preservative films is limited due to respective defects.
Disclosure of Invention
The invention aims to provide a waterproof breathable antibacterial DDS plastic film to solve the problems mentioned in the background technology.
In order to achieve the above purpose, the invention provides the following technical scheme:
a waterproof breathable antibacterial DDS plastic film comprises a resin material and a DDS medicament carrier arranged in the resin material; the DDS medicament carrier is prepared by deep processing of nano porous diatom minerals; the deep processing steps of the nano porous diatom mineral comprise: purifying, repairing holes, modifying and filling medicine; the hole repairing of the nano porous diatom mineral is hole expanding or hole shrinking; the modification of the nanoporous diatomaceous mineral comprises a hydrophobic modification; the nano porous diatom mineral is filled with a filling agent.
The invention is further described, the purification method of the nano porous diatom mineral adopts a roasting and acid leaching method; the hole expansion method of the nano porous diatom mineral adopts alkali etching; the method for shrinking the nano porous diatom mineral adopts TiCl 4 A liquid.
Further to the present invention, the hydrophobic modification agent of nanoporous diatom mineral employs coupling agent and activating agent; the coupling agent is one of silane, titanate and aluminum-titanium composite; the activating agent is one of stearic acid, polyvinyl ester, polyethylene glycol, polymethyl siloxane, acrylic acid, crotonic acid or vinyl acetate.
As further described in the present invention, the modifying function and modifying agent of the nanoporous diatom mineral can be selected from the following categories: magnetization induction modified-Fe 3O4, solubilization modified-peptide Peptides, hydrophilic modified-hydrophic, emulsification modified-selenoglycoprotein SEPS, fluorescence modified-Graphene Oxide, adhesion modified-ethoxysilane APTES, liposome membranization modified-Liposomes and temperature-sensitive modified-ATRP.
For further description of the present invention, the drenching agent is selected from the following categories: the drenching agent is selected from the following categories: nano platinum catalyst, peroxy compound, calcium peroxide, sodium peroxide, hydrogen peroxide, potassium superoxide, potassium permanganate, common salt, calcium chloride, nano titanium dioxide, nano silver, tetrazine, ethanol, budesonide, anthocyanidin, organic acid, lactein, allicin, gingerol, glycyrrhizin, tea polyphenol, peroxidase, allicin, laurin, konjac, sodium lactate, glacial acetic acid, potassium sorbate, meat bacteriostatic, honeysuckle, sophora japonica, freshness keeping, houttuyfonate, berberine, zinc ion, copper ion, silver ion, divalent iron species, propionic acid, benzoic acid, sorbic acid, nisin, thymol, thyme, thiosulfate, peroxidase, lysozyme, chaperone, allyl isothiocyanate, benomyl, chelating agent (EDTA), chlorophenol, nisin (nisin), as, zrO2, V2O3, cdS, seO2, gaP, snO2, as, WO3, fe2O3, RNA agent.
Further described herein, the RNA agent is one of mRNA, siRNA, miRNA, rRNA, sgRNA, and tRNA.
Among the above waterproof breathable food DDS plastic films, they can also be used in protective films for sanitary articles such as: diapers, sanitary napkins, facial masks, and the like.
The melt-blown cloth or non-woven fabric used on the sanitary article is made of plastic, so that the plastic film combined with the DDS medicament carrier in the design can be used.
Further describing the sanitary article of the present invention, the internal environment of the diaper/sanitary napkin is harsh, i.e., high heat, high humidity, bacteria-rich and mass-propagated. At present, the antibacterial agent is directly added into a packaging material, and the agent is directly contacted with skin and has poisoning or allergy problems. Before the product is used, the medicament begins to migrate/evaporate; when the active DDS paper diaper is used, the antibacterial agent is completely released at one time, no medicine can be released subsequently, and the fungi in the paper diaper are repeatedly planted again; when in use, the medicament is slowly released to generate long-term antibacterial effect.
The waterproof and breathable basement membrane of the existing paper diaper is a microporous or high-resolution microporous membrane made of a plastic film, and is poor in waterproofness and breathability. The DDS diatom mineral membrane principle of the invention is as follows: the minimum diameter of the water drop is 1000nm, the diameter of the water vapor molecule is 0.4nm, the diameter of the air molecule is 0.3nm, and the diameter of the micropore of the diatom mineral is 30 nm-500 nm. Water vapor and air readily pass through the diatom mineral pores while liquid water is blocked. According to the DDS diatom mineral disclosed by the invention, the medicament is coated in the diatom mineral cavity, and the medicament is not in direct contact with the skin, so that the poisoning or allergy problem is avoided.
Example 1: the DDS containing the calcium peroxide is decomposed in water to release a large amount of oxygen, the oxygen is beneficial to the skin, the oxygen increases the air circulation of the paper diaper, kills anaerobic bacteria, and generates gas in the cavity of the DDS, so that the water can be automatically drained and a ventilation channel is opened, the direct convection of air is strengthened, and the sultry and discomfort caused by air impermeability are reduced. The calcium peroxide is used as bactericide, disinfectant and antiseptic. The residual alkaline calcium hydroxide after the reaction of calcium peroxide and water is locked in the diatom shell cavity and does not contact with the skin.
Example 2: in the sanitary napkin in use, bacteria decompose blood/cell protein to generate putrefactive gases such as hydrogen sulfide, mercaptan, thioether, ammonia gas, methane, phenol, indole, bezoar, thioether, mercaptan, methyl ester and ethyl ester. The DDS is salt/calcium chloride and can absorb odorous gases such as hydrogen sulfide, ammonia, methane and the like, and residues of the DDS are locked in the diatom shell cavity after the DDS reacts with water and are not in contact with the skin. The DDS has the functions of paper diapers/sanitary towels: the air permeable, waterproof, antibacterial, deflating and inhaling functions enable the EMA (acquired Modified Atmosphere) in the paper diaper/sanitary towel to be adjusted and balanced.
A manufacturing process of a plastic film is used for manufacturing the waterproof breathable food DDS plastic film, and comprises the steps of purification, hole expansion, modification and drug filling, and specifically comprises the following steps:
a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiled 10% -15% hydrochloric acid for 5-10 hours;
2) Washing with ammonium hydroxide, and filtering for several times;
3) Placing into an oven, gradually heating to 700-900 deg.C, heating at a rate of 2-4 deg.C/min, baking for 4-8 hr, and air separating to obtain nanoporous diatom minerals with appropriate specification;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 20-40 minutes, and completely pumping air;
b. hole repairing:
5.1 Hole expansion): pouring the alkali etching liquid into a vacuum tank, expanding pores on the surface of the nano porous diatom mineral by the alkali etching liquid, and increasing the pore diameter of the micropores on the nano porous diatom mineral after alkali etching;
5.2 Shrinkage cavity): pouring TiCl4 liquid into a vacuum tank, accumulating TiO2 crystals in micropores on the surface of the nano porous diatom mineral, and shrinking the micropores on the surface of the nano porous diatom mineral;
selecting one step from the step (5.1) or the step (5.2) to carry out according to the pore diameter requirement of the micropores;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing the mixture into an oven to be gradually heated to 200 ℃, wherein the heating rate is 8-12 ℃/min, and the baking time is 4-8 hours;
8) Putting the nano porous diatom minerals subjected to hole repairing into a vacuum tank, vacuumizing for 20-40 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to one atmosphere for 5-15 minutes, heating to 700-900 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating to 90-110 ℃ for 2-4 hours, drying the hydrophobic modifier liquid, and leaving the hydrophobic modifier liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 20-40 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 30-50 ℃, fully attaching the drenching agent on the surface and the inner wall of the micropore of the nano porous diatom mineral, heating to 150-250 ℃ and drying to form a nano drug carrier DDS;
14 Nano drug carrier DDS and resin are put into an extruder to form a plastic film.
The first concrete scheme is as follows:
a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiling 12% hydrochloric acid for 8 hours;
2) Washing with ammonium hydroxide, and filtering for five times;
3) Placing the mixture into an oven to be gradually heated to 800 ℃, heating rate is 3 ℃/min, baking is carried out for 6 hours, and air is used for separating out nano porous diatom minerals with proper specifications;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
b. hole repairing:
5.1 Hole expansion): pouring an alkali etching liquid into a vacuum tank, expanding pores on the surface of the nano porous diatom mineral by the alkali etching liquid, and increasing the pore diameter of the pores on the nano porous diatom mineral from 2nm to 21nm after alkali etching;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing the mixture into an oven to be gradually heated to 200 ℃, wherein the heating rate is 10 ℃/min, and the baking time is 6 hours;
8) Putting the nano porous diatom minerals subjected to hole repairing into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to one atmosphere pressure for 10 minutes, heating to 800 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating at 100 ℃ for 3 hours, drying the hydrophobic modifier liquid, and leaving the liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 25 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 40 ℃, fully attaching the drenching agent on the surface and the inner wall of the micropore of the nano porous diatom mineral, heating to 200 ℃ and drying to form a nano drug carrier DDS;
14 The nano-drug carrier DDS and resin are put into an extruder to form a plastic film.
The second scheme is as follows:
a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiling 12% hydrochloric acid for 8 hours;
2) Washing with ammonium hydroxide, and filtering for five times;
3) Placing the mixture into an oven to be gradually heated to 800 ℃, heating rate is 3 ℃/min, baking is carried out for 6 hours, and air is used for separating out nano porous diatom minerals with proper specifications;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
b. hole repairing:
5.2 Shrinkage cavity): pouring TiCl4 liquid into a vacuum tank, accumulating TiO2 crystals in micropores on the surface of the nano porous diatom mineral, growing a plurality of small holes with the average size of 21nm from a 200nm large hole inner cavity, and shrinking the micropores on the surface of the nano porous diatom mineral;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing the mixture into an oven to be gradually heated to 200 ℃, wherein the heating rate is 10 ℃/min, and the baking time is 6 hours;
8) Putting the nano porous diatom minerals subjected to hole repairing into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to one atmosphere pressure for 10 minutes, heating to 800 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating to 100 ℃ for 3 hours, drying the hydrophobic modifier liquid, and leaving the hydrophobic modifier liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 25 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 40 ℃, fully attaching the drenching agent on the surface and the inner wall of the micropore of the nano porous diatom mineral, heating to 200 ℃ and drying to form a nano drug carrier DDS;
14 The nano-drug carrier DDS and resin are put into an extruder to form a plastic film.
The invention has the beneficial effects that:
the DDS is processed from nano-porous diatom minerals, and after the nano-porous diatom minerals are purified and expanded, hydrophobic and air-permeable modification is carried out, and the nano-porous diatom minerals are filled with medicaments, because the nano-porous diatom minerals have extremely strong physical adsorption performance (surface charge-3.05) and ion exchange performance, the medicaments can be effectively retained in preservative film products for a long time and cannot migrate or evaporate, when the preservative film contacts food, a nano-porous medicament carrier absorbs ethylene from the food and discharges the ethylene to the outside of the preservative film, in order to overcome the defects that the existing waterproof and air-permeable preservative films in the current market are low in air permeability, complex in preparation process and high in cost, the design realizes high air permeability, simple in preparation process and low cost, and compared with the traditional low-waterproof, low-air permeability, non-environmental-friendly and artificially synthesized films, the cost is low and environmental-friendly, and is a natural and environment-friendly plastic film (5 times of zeolite) with high water resistance.
Drawings
FIG. 1 is an enlarged structural view of the present invention;
FIG. 2 is an enlarged structural view of a cylindrical nanoporous diatom mineral according to the present invention;
FIG. 3 is an enlarged structural view of the spherical nanoporous diatom mineral according to the invention;
FIG. 4 isbase:Sub>A cross-sectional view A-A of FIG. 3;
fig. 5 is an enlarged structural view of B in fig. 4.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
as shown in fig. 1, a waterproof breathable antibacterial DDS plastic film comprises a resin material 1 and a DDS medicament carrier arranged in the resin material 1; the DDS medicament carrier is prepared by deep processing of nano porous diatom minerals 2; the deep processing steps of the nano-porous diatom mineral 2 comprise: purifying, repairing holes, modifying and filling the medicine; the hole repairing of the nano porous diatom mineral 2 is hole expansion or hole shrinkage; the modification of the nanoporous diatomaceous mineral 2 comprises a hydrophobic modification; the nano porous diatom mineral is filled with a filling agent 3 into the nano porous diatom mineral 2.
In the design, a roasting and acid leaching method is adopted as the purification method of the nano porous diatom mineral 2, and the purification degree of the nano porous diatom mineral 2 is high.
The pore-expanding method of the nano porous diatom mineral adopts alkali etching.
The method for shrinking the nano porous diatom mineral adopts TiCl 4 A liquid.
Obtaining a nano porous diatom mineral 2:
the method for obtaining the nano-porous diatom mineral 2 is cheap, and diatom fossil is excavated and diatom cells are cultured. The diatom is algae in the sea, is various and large in quantity, is the grassland in the sea, and creates oxygen on which 70% of earth life depends to live. Diatom mineral (or called amorphous silicon dioxide) is formed after diatom deposition and mineralization for billions of years, the diatom mineral is a nano-scale porous material, the diameter of a micropore is about 2nm to 5nm, the micropore is regularly and regularly arranged, and the number of the micropore on a unit area is 5000 to 6000 times larger than that of active carbon, so that the diatom mineral has extremely strong adsorption capacity. Prominent structural features of molecular lattice. Diatom minerals have extremely strong physical adsorption (xi surface charge-3.05) and ion exchange properties, and scientists have confirmed that diatom ooze in the arctic circle of oceans has absorbed 25% of mercury in atmospheric pollution over the past 150 years.
Structure introduction of nano-porous diatom mineral 2:
as shown in fig. 2 to 5, the structure of the nanoporous diatom mineral 2 is shown, the nanoporous diatom mineral 2 has a cylindrical and spherical structure, and the diatomaceous earth (diatomite) is siliceous biological sedimentary rock with opal as the main mineral component. Mainly composed of remains of diatoms. Is formed by the cell wall deposition of diatom. Diatoms are algae in the diatoms phylum, and the algal bodies are typically unicellular. The cell wall contains pectin and silicon dioxide, is hard, consists of two nested petals, and has patterns which are arranged in a radiation symmetry (radiation diatom meshes) or a left-right symmetry (feather meshes). After the diatom die, the remained cell walls are deposited into diatomite, the nano porous diatom mineral 2 is the bone hull wall 22 of the diatom die in the ocean or fresh water lake, and the nano porous diatom mineral 2 is a nano porous (hereinafter referred to as micropore 21) material, the size is 100 nm-300 nm, and the diatom has various shapes. The bone shell wall 22 supports the diatom cavity 23, and the ratio of the diatom cavity 23 to the volume ratio is up to 79.3%. The nano porous diatom mineral 2 is a specific electromagnetic medium, has the magnetic polarization physical characteristics which are not possessed by common natural media/conventional materials, has a plurality of pores and a large specific surface area, and the surface of the diatom bone shell wall 22 not only has a large amount of unsaturated residual bonds and hydroxyl groups in different bonding states, so that the diatom bone shell has high air permeability. In terms of optical characteristics, the food preservative has high reflection characteristics to ultraviolet light and visible light, and the food is prevented from aging.
Air permeability:
the nano porous diatom mineral 2 is implanted into the plastic resin film, and the crystallinity of the plastic can be destroyed by the nano diatom mineral, so that the plastic has more non-crystalline gaps, and the air permeability effect is achieved. The higher the crystallinity and the lower the air permeability of the plastic, taking oxygen penetrating HDPE as an example: crystallization rates of 60%, 69%, 81%; the air permeability is respectively reduced by 54.9, 20.9 and 10.6cm3 (STP) cm/cm2s (cm Hg)). The diatom mineral is porous and hollow, gaps exist between the diatom mineral and resin, and between the diatom mineral and diatom mineral, and fragments of the diatom mineral also fill the gaps to form air porous branches 6, air is communicated through the hollow/porous branches 6 to convey oxygen to food, and the oxygen inhibits/kills anaerobic bacteria. The gas emitted by the food is especially carbon dioxide, ethylene, amine gas etc. \8230, and can be smoothly discharged through the porous branches 6. The modified hydrophobicity of the diatom minerals prevents the water loss of food and maintains the freshness of the food. The diatom mineral has more micropores 21, uniform pore size distribution, air permeability, extremely small adsorbability, dust prevention, oil and water repellency, stable micro heat dissipation, chemical corrosion resistance, UV resistance and the like, can resist temperature and can continuously play an air permeability function under minus 40 to plus 150 degrees. The air permeability of diatom mineral is several times higher than that of plant fiber, zeolite and artificial fiber, and can reach 20000cm 3 Per square meter 24h 0.1MPa, 5000cm larger than the current artificially synthesized waterproof breathable film 3 Square meter per square meter 24h 0.1 MPa.
Table 1 total pore volume of diatomaceous mineral 1.18 is lower than that of zeolite 5.89, the interior of the diatomaceous mineral is empty, and the space in the cavity is large; the diatom mineral has pore size 14.55 larger than zeolite 8.94, which is favorable for air permeability, and the air permeability of diatom mineral is 5 times that of zeolite.
The product can be used for packaging food, greatly reduce the loss of nutrient substances of the food and ensure the flavor and the taste of raw food. Based on LDPE film, table 2 shows that the freshness keeping time of the breathable film permeated by diatom minerals is 45 days at the maximum, and the freshness keeping time of the typical LDPE sealing film is only 5 days.
Modification of the surface of diatom:
the diatom mineral is hydrophilic, so surface modification is needed, a surface chemical coating method is mainly adopted for modification, the shell surface and the inner wall of shell pores are improved to be hydrophobic, and the hydrophobic modification agent 24 of the nano-porous diatom mineral 2 adopts a coupling agent and an activating agent; the coupling agent is one of silane, titanate and aluminum-titanium composite; the activating agent is one of stearic acid, polyvinyl ester, polyethylene glycol, polymethyl siloxane, acrylic acid, crotonic acid or vinyl acetate.
The modifier 24 can be used as a modifier with other functions, and can be selected from the following categories according to actual needs: the material comprises magnetic induction modified Fe3O4, solubilizing modified Peptides, hydrophilic modified hydrophyllic, emulsification modified selenoglycoprotein SEPS, fluorescent modified Graphene Oxide (GO), adhesion modified ethoxysilane APTES, liposome membranization modified liposomees, temperature-sensitive modified ATRP and the like.
Example 1: the modified medicament 24 adopts ethoxysilane APTES (3-aminopropyltriethoxysilane), so that the nanoporous diatom mineral 2 can be easily attached to meat products.
Example 2: the modified medicament 24 adopts tetramethylpiperidine oxide tetramethylpiperidine, TEMPO-APTES, so that the nanoporous diatom mineral 2 prevents the oxidation of the meat products by the medicament.
Example 3: the modification agent 24 adopts Atom Transfer Polymerization (Atom Transfer Polymerization) to generate a valve structure on the micropores 21 of the nanoporous diatom mineral 2, and the valve structure expands to close the pores at high temperature and contracts to open the pores at low temperature. The channels are opened at a specific temperature to release the drug. For example, the siRNA drug is released below a specific temperature of 12 ℃, so that the metabolism of vegetables and fruits is slow. After being packed, vegetables and fruits must be put into a refrigerator as soon as possible to be preserved at the temperature below 12 ℃, and the 3 nanometer platinum catalyst is automatically released and filled at low temperature.
Example 4: the modified medicament 24 adopts fluorescence-Graphene Oxide (GO), so that the diatom DDS presents fluorescence, the existence of the diatom DDS can be observed through illumination, and the uniformity and the density of the diatom DDS spread on the preservative film can be checked. It is also possible to check whether they remain on the food.
Use of drench 3:
according to actual functional requirements, the drenching agent 3 is selected from the following categories: the drenching agent is selected from the following categories: nano platinum catalyst, peroxy compound, calcium peroxide, sodium peroxide, hydrogen peroxide, potassium superoxide, potassium permanganate, common salt, calcium chloride, nano titanium dioxide, nano silver, tetrazine, ethanol, budesonide, anthocyanidin, organic acid, lactein, allicin, gingerol, glycyrrhizin, tea polyphenol, peroxidase, allicin, laurin, konjac, sodium lactate, glacial acetic acid, potassium sorbate, meat bacteriostatic, honeysuckle, sophora japonica, freshness keeping, houttuyfonate, berberine, zinc ion, copper ion, silver ion, divalent iron species, propionic acid, benzoic acid, sorbic acid, nisin, thymol, thyme, thiosulfate, peroxidase, lysozyme, chaperone, allyl isothiocyanate, benomyl, chelating agent (EDTA), chlorophenol, nisin (nisin), as, zrO2, V2O3, cdS, seO2, gaP, snO2, as, WO3, fe2O3, RNA agent.
The RNA medicament is one of mRNA, siRNA, miRNA, rRNA, sgRNA and tRNA.
Example 1: the filling agent 3 adopts a nano platinum catalyst (containing a nano palladium catalyst and a nano auxiliary catalyst), and the nano platinum catalyst can adsorb and decompose ethylene gas in a large amount, inhibit the respiration of fruits and vegetables, keep the freshness of the fruits and vegetables for a longer time and reduce the loss of vitamins to about 1/3 of that of the conventional common fruit and vegetable box. The nano palladium catalyst has good antibacterial effect, has the antibacterial capability on staphylococcus aureus and escherichia coli of more than 99 percent, effectively solves the problem of fruit and vegetable decay and deterioration caused by microbial infection, and prolongs the fresh-keeping time of the fruit and vegetable. The nano platinum catalyst has the advantages that the nano porous structure medicament carrier has extremely strong physical adsorption performance (surface charge of-3.05) and ion exchange performance, so that the filling medicament 3 can be effectively retained in the diatom minerals for a long time and cannot migrate or evaporate to food. The porous structure of the diatom mineral allows platinum nanoparticles with a size of 20 nanometers to be uniformly distributed in a very small volume of the diatom mineral, locking the platinum catalyst, and also avoiding potential contamination of food by platinum nanoparticles.
Example 2: the drench 3 adopts siRNA, 22nt-siRNA generated by two coding genes NIA1 and NIA2 of the siRNA induces the amplification of gene silencing effect and can induce the translation inhibition of the gene. These 22 nt-siRNAs accumulate preferentially under environmental stress, especially siRNAs from NIA1 and NIA2 genes, thereby inhibiting fruit/vegetable growth by limiting gene translation. In ein5 dcl4 and ski2 dcl4, stress responses of vegetables and fruits such as ABA signal pathway or stress response pathway are activated by siRNA, and growth responses of vegetables and fruits such as photosynthesis and cell division are inhibited.
The siRNA does not participate in the biological growth of the vegetables, fruits and meat, is a product of RNAi, and has the effects of inhibiting the metabolic activity of the vegetables, fruits and meat, inhibiting the infection of anaerobic bacteria and inhibiting the metabolism of the vegetables, fruits and meat, wherein the slower the metabolism is, the longer the preservation time is. RNAi interference, which uses double-stranded RNA (dsRNA) with homology to induce silence of gene activity of target anaerobe with sequence specificity, and rapidly blocks the anaerobe activity. The siRNA degrades/blocks RNA messenger (mRNA) of vegetables and fruits in an RNA silencing pathway, and plays a role in slowing metabolism of the vegetables and fruits.
Example 3: the filling agent 3 adopts Zn ions, the bacteriostasis rate of the Zn ions is as high as 91 percent, and the propagation of escherichia coli/golden yellow staphylococcus in meat products can be prevented. Zn ion is an essential element for human body, participates in metabolism of more than 80 enzymes of human body, and is an essential element for growth and development of human body, reproductive heredity, immune endocrine, nervous system and humoral regeneration. Zinc ions are put into the DDS preservative film to be sterilized and preserved, and the DDS preservative film is beneficial to the human body and two at a time.
The plastic film structure can be applied to waterproof and breathable components such as food preservative films, preservative boxes, rain clothes, caps, tents and the like, and can also be applied to sanitary products such as sanitary towels, paper diapers and the like.
The manufacturing process of the waterproof breathable food DDS plastic film comprises the following specific processing steps:
the first scheme is as follows:
a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiling 12% hydrochloric acid for 8 hours;
2) Washing with ammonium hydroxide, and filtering for five times;
3) Placing the mixture into an oven to be gradually heated to 800 ℃, heating rate is 3 ℃/min, baking is carried out for 6 hours, and air is used for separating out nano porous diatom minerals with proper specifications;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
b. hole repairing:
5.1 Hole expansion): pouring an alkali etching liquid into a vacuum tank, expanding pores on the surface of the nano porous diatom mineral by the alkali etching liquid, and increasing the pore diameter of the micropores on the nano porous diatom mineral from 2nm to 21nm after alkali etching;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing the mixture into an oven to be gradually heated to 200 ℃, wherein the heating rate is 10 ℃/min, and the baking time is 6 hours;
8) Placing the nano porous diatom minerals after hole repairing into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to one atmosphere pressure for 10 minutes, heating to 800 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating at 100 ℃ for 3 hours, drying the hydrophobic modifier liquid, and leaving the liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 25 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 40 ℃, fully attaching the drenching agent on the surface and the inner wall of the micropore of the nano porous diatom mineral, heating to 200 ℃ and drying to form a nano drug carrier DDS;
14 The nano-drug carrier DDS and resin are put into an extruder to form a plastic film.
Scheme II: a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiling 12% hydrochloric acid for 8 hours;
2) Washing with ammonium hydroxide, and filtering for five times;
3) Placing the mixture into an oven to be gradually heated to 800 ℃, heating rate is 3 ℃/min, baking is carried out for 6 hours, and air is used for separating out nano porous diatom minerals with proper specifications;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
b. hole repairing:
5.2 Shrinkage cavity): pouring TiCl4 liquid into a vacuum tank, accumulating TiO2 crystals in micropores on the surface of the nano porous diatom mineral, growing a plurality of small holes with the average size of 21nm from a 200nm large hole inner cavity, and shrinking the micropores on the surface of the nano porous diatom mineral;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing the mixture into an oven to be gradually heated to 200 ℃, wherein the heating rate is 10 ℃/min, and the baking time is 6 hours;
8) Placing the nano porous diatom minerals after hole repairing into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to one atmosphere for 10 minutes, heating to 800 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating to 100 ℃ for 3 hours, drying the hydrophobic modifier liquid, and leaving the hydrophobic modifier liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 25 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 40 ℃, fully attaching the drenching agent on the surfaces and inner walls of the micropores of the nano porous diatom minerals, and heating to 200 ℃ for drying to form a nano drug carrier DDS;
14 The nano-drug carrier DDS and resin are put into an extruder to form a plastic film.
The above description is not intended to limit the technical scope of the present invention, and any modification, equivalent change and modification of the above embodiments according to the technical spirit of the present invention are still within the technical scope of the present invention.
Claims (10)
1. The utility model provides a waterproof ventilative antibiotic DDS plastic film which characterized in that: comprises a resin material and a DDS medicament carrier arranged in the resin material; the DDS medicament carrier is prepared by deep processing of nano porous diatom minerals; the deep processing steps of the nano porous diatom mineral comprise: purifying, repairing holes, modifying and filling medicine; the hole repairing of the nano porous diatom mineral is hole expanding or hole shrinking; the modification of the nanoporous diatomaceous mineral comprises a hydrophobic modification; the nano porous diatom mineral is filled with a filling agent.
2. The waterproof breathable antibacterial DDS plastic film of claim 1, wherein: the purification method of the nano porous diatom mineral adopts a roasting and acid leaching method; the hole expansion method of the nano porous diatom mineral adopts alkali etching; the method for shrinking the nano porous diatom mineral adopts TiCl 4 A liquid.
3. A waterproof breathable antibacterial DDS plastic film as claimed in claim 1 wherein: the hydrophobic modification agent of the nano porous diatom mineral adopts a coupling agent and an activating agent; the coupling agent is one of silane, titanate and aluminum-titanium composite; the activating agent is one of stearic acid, polyvinyl ester, polyethylene glycol, polymethyl siloxane, acrylic acid, crotonic acid or vinyl acetate.
4. The waterproof breathable antibacterial DDS plastic film of claim 1, wherein: the modifying function and modifying agent of the nano porous diatom mineral can be selected from the following categories: the preparation method comprises the following steps of magnetization induction modification-Fe 3O4, solubilization modification-peptide Peptides, hydrophilic modification-hydrophyllic, emulsification modification-selenoglycoprotein SEPS, fluorescence modification-graphene oxide, adhesion modification-ethoxysilane APTES, liposome membranization modification-Liposomes and temperature-sensitive modification-ATRP.
5. The waterproof breathable antibacterial DDS plastic film of claim 1, wherein: the drenching agent is selected from the following categories: nano platinum catalyst, peroxy compound, calcium peroxide, sodium peroxide, hydrogen peroxide, potassium superoxide, potassium permanganate, salt, calcium chloride, nano titanium dioxide, nano silver, tetrazine, ethanol, budesonide, anthocyanins, organic acids, lactein, allicin, gingerol, glycyrrhizin, tea polyphenol, peroxidase, allicin, laurin, konjac, glacial acetic acid, potassium sorbate, meat bacteriostasis, honeysuckle, sophora japonica, freshness keeping, houttuyfonate, berberine, zinc ions, copper ions, silver ions, divalent iron species, propionic acid, benzoic acid, sorbic acid, nisin, thymol, thyme, thiosulfate, peroxidase, lysozyme, sodium lactate, allyl isothiocyanate, benomyl, chelating agent (EDTA), chlorophenol, nisin (nisin), as, zrO2, V2O3, cdS, seO2, gaP, snO2, as, WO3, fe2O3, znS, and RNA medicament.
6. The waterproof breathable antibacterial DDS plastic film of claim 5, wherein: the RNA medicament is one of mRNA, siRNA, miRNA, rRNA, sgRNA and tRNA.
7. A sanitary product, characterized in that: the DDS plastic film comprises a sanitary article body and a protective film arranged on the sanitary article body, wherein the protective film adopts the DDS plastic film for the waterproof and breathable food of any one of claims 1-6.
8. A plastic film manufacturing process for manufacturing the waterproof breathable food DDS plastic film of any one of claims 1-6, which is characterized by comprising the steps of purification, hole expansion, modification and drug filling, and specifically comprises the following steps:
a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiled 10% -15% hydrochloric acid for 5-10 hours;
2) Washing with ammonium hydroxide, and filtering for several times;
3) Placing into an oven, gradually heating to 700-900 deg.C, heating at a rate of 2-4 deg.C/min, baking for 4-8 hr, and air separating to obtain nanoporous diatom minerals with appropriate specification;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 20-40 minutes, and completely pumping air;
b. hole repairing:
5.1 Hole expansion): pouring an alkali etching liquid into a vacuum tank, expanding pores on the surface of the nano porous diatom mineral by the alkali etching liquid, and increasing the pore diameter of the pores on the nano porous diatom mineral after alkali etching;
5.2 Shrinkage cavity): mixing TiCl 4 Pouring the liquid into a vacuum tank, accumulating TiO2 crystals in micropores on the surface of the nano porous diatom mineral, and shrinking the micropores on the surface of the nano porous diatom mineral;
selecting one step from the step (5.1) or the step (5.2) to carry out according to the pore diameter requirement of the micropores;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing into an oven, gradually heating to 200 deg.C, heating at a rate of 8-12 deg.C/min, and baking for 4-8 hr;
8) Placing the nano porous diatom minerals after hole repairing into a vacuum tank, vacuumizing for 20-40 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to atmospheric pressure for 5-15 minutes, heating to 700-900 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating to 90-110 ℃ for 2-4 hours, drying the hydrophobic modifier liquid, and leaving the hydrophobic modifier liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 20-40 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 30-50 ℃, fully attaching the drenching agent on the surface of the nano porous diatom mineral and the inner wall of the micropore, and heating to 150-250 ℃ for drying to form a nano drug carrier DDS;
14 The nano-drug carrier DDS and resin are put into an extruder to form a plastic film.
9. The process for manufacturing a plastic film according to claim 8, wherein: the method comprises the following specific steps:
a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiling 12% hydrochloric acid for 8 hours;
2) Washing with ammonium hydroxide, and filtering for five times;
3) Placing the mixture into an oven to be gradually heated to 800 ℃, heating rate is 3 ℃/min, baking is carried out for 6 hours, and air is used for separating out nano porous diatom minerals with proper specifications;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
b. hole repairing:
5.1 Hole expansion): pouring an alkali etching liquid into a vacuum tank, expanding pores on the surface of the nano porous diatom mineral by the alkali etching liquid, and increasing the pore diameter of the pores on the nano porous diatom mineral from 2nm to 21nm after alkali etching;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing the mixture into an oven to be gradually heated to 200 ℃, wherein the heating rate is 10 ℃/min, and the baking time is 6 hours;
8) Putting the nano porous diatom minerals subjected to hole repairing into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to one atmosphere pressure for 10 minutes, heating to 800 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating to 100 ℃ for 3 hours, drying the hydrophobic modifier liquid, and leaving the hydrophobic modifier liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 25 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 40 ℃, fully attaching the drenching agent on the surfaces and inner walls of the micropores of the nano porous diatom minerals, and heating to 200 ℃ for drying to form a nano drug carrier DDS;
14 The nano-drug carrier DDS and resin are put into an extruder to form a plastic film.
10. The process for manufacturing a plastic film according to claim 8, wherein: the method comprises the following specific steps:
a. and (3) purification:
1) Soaking and washing the nano porous diatom mineral in boiling 12% hydrochloric acid for 8 hours;
2) Washing with ammonium hydroxide, and filtering for five times;
3) Placing the mixture into an oven to be gradually heated to 800 ℃, heating rate is 3 ℃/min, baking is carried out for 6 hours, and air is used for separating out nano porous diatom minerals with proper specifications;
4) Placing the sorted nano porous diatom minerals into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
b. hole repairing:
5.2 Shrinkage cavity): pouring TiCl4 liquid into a vacuum tank, accumulating TiO2 crystals in micropores on the surface of the nano porous diatom mineral, growing a plurality of small holes with the average size of 21nm from a 200nm large hole inner cavity, and shrinking the micropores on the surface of the nano porous diatom mineral;
6) Washing with ammonium hydroxide, and filtering for several times;
7) Placing the mixture into an oven to be gradually heated to 200 ℃, wherein the heating rate is 10 ℃/min, and the baking time is 6 hours;
8) Putting the nano porous diatom minerals subjected to hole repairing into a vacuum tank, vacuumizing for 30 minutes, and completely pumping air;
c. modification:
9) Stopping vacuumizing, and pouring the hydrophobic modifier liquid into a vacuum tank;
10 Pressurizing the vacuum tank to one atmosphere pressure for 10 minutes, heating to 800 ℃, and fully attaching the hydrophobic modifier liquid to the whole surface of the diatom mineral under high pressure;
11 Decompressing the vacuum tank, taking out the nano porous diatom mineral, heating to 100 ℃ for 3 hours, drying the hydrophobic modifier liquid, and leaving the hydrophobic modifier liquid on the surface of the diatom cavity to form a hydrophobic air-permeable passage;
d. filling the medicine:
12 Placing the nano porous diatom mineral into a vacuum tank, and vacuumizing for 25 minutes;
13 Stopping vacuumizing, putting the drenching agent into a vacuum tank, heating to 40 ℃, fully attaching the drenching agent on the surfaces and inner walls of the micropores of the nano porous diatom minerals, and heating to 200 ℃ for drying to form a nano drug carrier DDS;
14 The nano-drug carrier DDS and resin are put into an extruder to form a plastic film.
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