CN112227113B - Antibacterial and moistureproof carton - Google Patents
Antibacterial and moistureproof carton Download PDFInfo
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- CN112227113B CN112227113B CN202011147981.4A CN202011147981A CN112227113B CN 112227113 B CN112227113 B CN 112227113B CN 202011147981 A CN202011147981 A CN 202011147981A CN 112227113 B CN112227113 B CN 112227113B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/40—Multi-ply at least one of the sheets being non-planar, e.g. crêped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/08—Corrugated paper or cardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D13/00—Containers having bodies formed by interconnecting two or more rigid, or substantially rigid, components made wholly or mainly of the same material, other than metal, plastics, wood, or substitutes therefor
- B65D13/04—Containers having bodies formed by interconnecting two or more rigid, or substantially rigid, components made wholly or mainly of the same material, other than metal, plastics, wood, or substitutes therefor of paper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/26—All layers being made of paper or paperboard
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Abstract
An antibacterial moisture-proof carton relates to the technical field of packaging. The invention aims to solve the problems that the effect of an antibacterial agent taking walnut green husks as a plant source is poor, a method for applying the antibacterial agent to a carton, particularly a corrugated case, is unavailable, and the mechanical property and the moisture-proof effect of the existing corrugated case are poor. An antibacterial damp-proof carton is a corrugated case, and the corrugated case sequentially comprises inner paper, a first buffer layer, a second buffer layer, corrugated medium paper and surface paper from inside to outside; the moisture-proof paper is adhered to the outer surface of the surface paper of the corrugated box, and the walnut green husk antibacterial agent is sprayed on the surface of the corrugated medium paper and the inner surface of the surface paper of the corrugated box.
Description
Technical Field
The invention relates to the technical field of packaging, in particular to an antibacterial and moistureproof carton.
Background
Plant-derived antibacterial agents are safer to humans than chemical antibacterial agents because they are derived from natural plants and do not contain chemical agents, but they have problems such as unstable antibacterial effects and difficulty in obtaining the source.
Walnut green husk, also called Qinglongyi, is the green exocarp of immature fruit of juglandaceae plant Juglans mandshurica (Juglans MandshuricaM.) and Juglans regia (Juglans regia L.), and modern pharmacological studies show that walnut green husk has the activities of resisting tumor, easing pain, resisting bacteria, diminishing inflammation, resisting oxidation and the like. But the walnut green seedcase is singly adopted as an antibacterial agent and has poor broad-spectrum antibacterial property, and the research reports of the combined use of the walnut green seedcase and a plant source bacteriostatic agent are few at present. And there are few reports of its application to cartons, especially corrugated boxes.
The corrugated case is made of corrugated board, wax-coated corrugated board and other materials, is a packaging container with certain rigidity and strength, but the existing corrugated case has poor mechanical properties. The main component of the paper is paper fiber with strong water absorption and generally has a porous structure, so the paper is easy to be wetted and easy to mildew when the humidity is more than 12 percent. Therefore, the corrugated case needs to have good strength and good waterproof performance and mildew resistance, and no relevant research is carried out on the preparation of the antibacterial agent by adopting the natural plant source antibacterial and mildew-proof agent and the treatment of the corrugated case by using the damp-proof paper.
Disclosure of Invention
The invention aims to solve the problems that the broad spectrum of an antibacterial agent taking walnut green husks as a plant source is poor, the method for applying the antibacterial agent to a carton, particularly a corrugated case, is not available, and the mechanical property and the moisture-proof effect of the existing corrugated case are poor. And provides an antibacterial moisture-proof carton.
The invention relates to an antibacterial moisture-proof carton which is a corrugated box, wherein the corrugated box sequentially comprises inner paper, a first buffer layer, a second buffer layer, corrugated medium paper and surface paper from inside to outside; the first buffer layer and the second buffer layer are formed by closely arranging a plurality of rows of arches, the arch of the first buffer layer is opposite to the arch opening direction of the second buffer layer, and the arch surfaces are attached in a staggered manner; the corrugated core paper is composed of a plurality of closely arranged prismatic tables arranged on a bottom plate, and the upper bottom surfaces of the prismatic tables are attached to the surface paper; the moisture-proof paper is adhered to the outer surface of the surface paper of the corrugated box, and the walnut green husk antibacterial agent is sprayed on the surface of the corrugated medium paper and the inner surface of the surface paper of the corrugated box;
the walnut green husk antibacterial agent consists of 8-20 parts by weight of walnut green husk extract, 5-15 parts by weight of coptis chinensis extract, 2-10 parts by weight of wormwood extract and 1-8 parts by weight of clove extract;
the walnut green husk extract is obtained according to the following method:
drying walnut green seedcases to constant weight, crushing and sieving the dried walnut green cases by a sieve of 80-100 meshes, uniformly mixing the sieved walnut green cases with ethanol according to the liquid-material ratio of 20-25: 1 to obtain a mixed solution, then adding sodium hexametaphosphate in an amount which is 0.8-1.2 times of the volume of the mixed solution, uniformly mixing, and extracting for 120min at the temperature of 70 ℃ and under the microwave power of 700-750W, wherein the volume percentage content of the ethanol is 50%, and the concentration of the extract is 15-25 mg/mL;
the moisture-proof paper is obtained according to the following steps:
pulping plant fibers, then adding the pulped plant fibers into water to obtain a plant cellulose solution with the mass percent of 4% -5%, adding schisandra chinensis nanocellulose into the water to obtain a schisandra chinensis nanocellulose solution with the mass percent of 4% -5%, mixing the schisandra chinensis nanocellulose solution with the mass percent of 4% -5% with the plant cellulose solution with the mass percent of 4% -5% according to the volume ratio of 1:5, and carrying out hot-pressing drying to obtain composite paper;
step two, mixing butanetetracarboxylic acid, triethanolamine and deionized water to obtain a mixed solution of the butanetetracarboxylic acid and the triethanolamine, then soaking the composite paper into the mixed solution of the butanetetracarboxylic acid and the triethanolamine for 10-20 min, and drying the soaked composite paper to obtain modified composite paper;
the molar ratio of the butane tetracarboxylic acid to the deionized water is 1 (30-50); the molar ratio of the butane tetracarboxylic acid to the triethanolamine is 1 (1-5);
step three, dropwise adding a sulfuric acid solution with the concentration of 4-6 mol/L into a sodium silicate solution with the concentration of 1-2 mol/L until the pH value is 2-4, then adjusting the pH value to be neutral, filtering to obtain silicon dioxide, adding the silicon dioxide into ethanol for dispersing, and then adding KH550 to obtain a modified silicon dioxide solution;
the mass ratio of the mol of the sodium silicate in the sodium silicate solution to the KH550 is 1mol (3-7) g;
and step four, spraying the modified silicon dioxide solution on one side of the modified composite paper to obtain the moisture-proof paper.
Further, the coptis chinensis extract is obtained according to the following steps:
1) cleaning Coptidis rhizoma, cutting, and grinding into powder; adding methanol-hydrochloric acid solution for dissolving, carrying out ultrasonic treatment for 30-40 min, cooling to room temperature, and filtering with a 0.22 mu m microporous filter membrane; wherein the volume ratio of methanol to hydrochloric acid in the methanol-hydrochloric acid solution is 100: 1;
2) using Ca (OH)2Adjusting the pH value of the filtrate obtained in the step 1) to 5-6, continuously stirring during the adjustment of the pH value, then filtering, filtering the filtrate, passing the filtered filtrate through a 0.22 mu m microporous filter membrane, adding HCl into the filtrate to adjust the pH value to 1-2, adding a sodium chloride solution with the mass percent of 5% to dissolve the filtrate, refrigerating the filtrate overnight in a refrigerator, and drying a filter cake at 50 ℃; wherein the mass volume ratio of the sodium chloride in the 5% sodium chloride solution to the filtrate is 1g:10 mL.
Further, the wormwood extract is obtained according to the following steps:
taking 8-month middle ten-day wormwood, drying, adding boiled distilled water according to the mass-volume ratio of 1g: 5-6 mL, adding saturated lime water under stirring to adjust the pH value to 8-9, heating to 100 ℃ under the pH value, keeping for 40-50 min, adjusting the pH value to 4-5 under the stirring condition of 80-90 ℃, standing, performing suction filtration, washing and precipitating until the washing liquor is neutral, and drying at 50-60 ℃ to constant weight; collecting the dried substances, adding boiled distilled water according to the mass-to-volume ratio of 1g: 400-500 mL, heating, boiling and keeping for 20min until the solution is clear, filtering while hot, collecting filtrate, cooling to room temperature, performing suction filtration, washing the precipitate with water until the washing solution is neutral, and drying at 50-60 ℃ to constant weight to obtain the wormwood extract.
Further, the clove extract is obtained by supercritical extraction, and the supercritical extraction conditions are as follows: the temperature is 44 ℃, the pressure is 12MPa, the time is 1-2 h, and the carbon dioxide flow is 15-20L/h.
Further, the walnut green husk antibacterial agent consists of 8-15 parts by weight of walnut green husk extract, 5-10 parts by weight of coptis chinensis extract, 2-8 parts by weight of wormwood extract and 1-5 parts by weight of clove extract.
Further, the schisandra chinensis nanocellulose in the step one is prepared according to the following steps: putting the schisandra chinensis rhizome powder into a sodium hypochlorite solution with the concentration of 0.5-1 wt%, adjusting the pH to 4-5 by adopting glacial acetic acid, and carrying out heating reflux reaction for 4-6 h to obtain a primary reaction product; the volume ratio of the mass of the schisandra chinensis rhizome powder to the sodium hypochlorite solution with the concentration of 0.5-1 wt% is 3g (10-30) mL; the schisandra chinensis root and stem powder is obtained by drying schisandra chinensis roots and stems until the water content is lower than 10%, and then crushing the dried schisandra chinensis roots and stems to obtain schisandra chinensis root and stem powder with the particle size of 200-300 meshes; secondly, performing suction filtration on the primary reaction product, washing with deionized water until the filtrate obtained by suction filtration is neutral to obtain a solid product, then putting the solid product into a sodium sulfite solution with the concentration of 5-10 wt%, and performing heating reflux reaction for 4-6 h to obtain a secondary reaction product; the volume ratio of the mass of the solid product to the sodium sulfite solution with the concentration of 5-10 wt% is 1.5g (4-20) mL; thirdly, performing suction filtration on the secondary reaction product, washing the secondary reaction product for 1-3 times by using deionized water to obtain a washed solid product, placing the washed solid product into a NaOH aqueous solution with the mass fraction of 5-30%, stirring and reacting the solid product for 30-90 min at the temperature of 40-100 ℃, and performing centrifugal separation to obtain the schisandra chinensis nanocellulose; the volume ratio of the mass of the washed solid product to the NaOH aqueous solution with the mass fraction of 5-30% is 1g (10-30) mL.
Further, the plant fiber in the step one is hardwood dissolving pulp with lignin and hemicellulose removed.
Further, in the second step, the impregnated composite paper is dried at the temperature of 40-60 ℃ for 10-20 min, and then dried at the temperature of 80-100 ℃ for 2-5 min.
And further, spraying the modified silicon dioxide solution on one side of the modified composite paper by using a spray gun in the fourth step under the conditions that the distance between the spray gun and the modified composite paper is 15-20 cm and the spraying pressure is 0.2MPa until the spraying thickness is 1-3 microns.
The invention has the following beneficial effects:
the method of the invention uses the walnut green husk extract and the coptis extract as main bacteriostatic components in a combined way, and can obviously enhance the antibacterial and antifungal effects of the walnut green husk extract. The added wormwood extract and clove extract can improve the antibacterial types, such as 10 gram-positive bacteria including bacillus anthracis, alpha-hemolytic streptococcus, B-hemolytic streptococcus, diphtheria bacillus, pseudodiphtheria bacillus, pneumococcus diplococcus, staphylococcus aureus, staphylococcus citrullus, staphylococcus albus, bacillus subtilis and the like, especially can obviously improve the antifungal effect of the antibacterial agent, and the added clove has obvious inhibition effect on pathogenic fungi.
The composite paper is prepared by taking the schisandra chinensis nanocellulose as one of the raw materials, the schisandra chinensis is a perennial magnolia, and the schisandra chinensis nanocellulose retains the schisandra chinensis lignan, has good oxidation resistance and extremely high antibacterial performance.
Then, the composite paper is further subjected to hydrophobic modification, active groups are firstly introduced, and then-NH is added2The composite paper is introduced to the surface of the silicon dioxide, and the silicon dioxide are combined in a reaction mode, so that one side of the composite paper has super-hydrophobic property, and the contact angle can reach over 155 degrees.
The bottom plate of the corrugated medium paper is provided with the plurality of closely arranged prismatic tables, and a plurality of surfaces of the prismatic tables are mutually pulled and supported, compared with the traditional corrugated medium paper, the support on two surfaces is more stable and is not easy to damage, and the arch of the first buffer layer and the arch of the second buffer layer are opposite in opening direction and are in staggered fit, so that two tangent points exist in the mutual fit process of the arch of the first buffer layer and the arch of the second buffer layer, and in the positive impact process, the two tangent points jointly offset, mutually restrict and disperse force according to the direction of force, and the arch surface has elasticity, and when one side arch deforms, the other side has two arches to support the other side, therefore, the corrugated box is improved in the penetration strength, the burst strength and the edge pressing strength through the design of a special structure.
According to the invention, the antibacterial agent is sprayed on the inner layers of the corrugated medium paper and the surface paper of the corrugated box, so that bacteria can be effectively prevented from further corroding the inner paper and the buffer layer of the corrugated box to damage the inner paper and the buffer layer, and the compression resistance of the corrugated box is reduced.
The invention combines the antibacterial agent and the moisture-proof paper to be used on the corrugated case, which can obviously reduce the mildew of the paper case, as is well known, the mildew of the paper case is mainly caused by the mass proliferation of fungi and mould, the environment with proper humidity temperature can promote the rapid proliferation of the fungi and mould, one side of the moisture-proof paper prepared by the invention, which is not subjected to hydrophobic modification, is directly adhered on the paper case, the walnut green husk antibacterial agent prepared by the invention is sprayed on the surface of the corrugated medium paper, the corrugated case has antibacterial moisture resistance through hydrophobicity and bacteriostasis, the moisture is prevented from entering the case body in a super-hydrophobic mode, the water absorption of the case body is reduced, thereby reducing the generation of the growth environment of the fungi, and the moisture is prevented from entering the case body through the super-hydrophobic moisture-proof paper, simultaneously, the moisture is prevented from entering the case body with strains, even if the strains enter the case body, the antibacterial agent is sprayed on the inner layer, so that the antibacterial effect is effectively realized. Therefore, the scheme of the invention is particularly suitable for easily rotten and rotten substances such as fruits, fresh fruits and the like. The scheme of the invention does not need to change the placement environment of the paper box too much, saves the cost and has wide market application value.
Drawings
Fig. 1 is a schematic structural view of a corrugated box according to embodiment 1;
FIG. 2 is a schematic view of the structure of the paper and the first buffer layer in example 1;
fig. 3 is a schematic structural view of a corrugated medium paper of example 1;
FIG. 4 is a schematic view of the structure of the truncated pyramid in example 1.
Detailed Description
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
To make the objects, aspects and advantages of the embodiments of the present invention more apparent, the following detailed description clearly illustrates the spirit of the disclosure, and any person skilled in the art, after understanding the embodiments of the disclosure, may make changes and modifications to the technology taught by the disclosure without departing from the spirit and scope of the disclosure.
The exemplary embodiments of the present invention and the description thereof are provided to explain the present invention and not to limit the present invention.
The beneficial effects of the present invention are demonstrated by the following examples:
example 1
Specifically describing the present embodiment with reference to fig. 1 to 4, the antibacterial and moisture-proof carton of the present embodiment is a corrugated carton, and the corrugated carton sequentially comprises an inner paper 1, a first buffer layer 2-1, a second buffer layer 2-2, a corrugated medium 3, and a surface paper 4 from inside to outside; the first buffer layer 2-1 and the second buffer layer 2-2 are formed by closely arranging a plurality of rows of arches, the arch of the first buffer layer 2-1 is opposite to the arch opening direction of the second buffer layer 2-2, and the arch surfaces are attached in a staggered manner; the corrugated medium paper 3 is composed of a plurality of closely arranged prismatic tables 3-2 arranged on a bottom plate 3-1, and the upper bottom surfaces of the prismatic tables 3-2 are attached to the surface paper 4; the moisture-proof paper is adhered to the outer surface of the surface paper 4 of the corrugated box, and the walnut green husk antibacterial agent is sprayed on the surface of the corrugated medium paper 3 and the inner surface of the surface paper 4 of the corrugated box;
the walnut green husk antibacterial agent consists of a walnut green husk extract, a coptis chinensis extract, a wormwood extract and a clove extract;
the walnut green husk extract is obtained according to the following method:
drying walnut green husks to constant weight, crushing and sieving the dried walnut green husks by a sieve of 80 meshes, uniformly mixing the sieved walnut green husks with ethanol according to the liquid-material ratio of 25:1 to obtain a mixed solution, then adding sodium hexametaphosphate in an amount which is 1.0 time of the volume of the mixed solution, uniformly mixing, and extracting for 120min at the temperature of 70 ℃ and the microwave power of 700W, wherein the volume percentage content of the ethanol is 50%, and the concentration of the extract is 20 mg/mL. The yield of the extracted walnut polyphenol is 4.82mg/g, and the extraction effects respectively reach remarkable (P is less than 0.05) and extremely remarkable (P is less than 0.01) levels. The walnut polyphenol can be effectively extracted by adopting the method, so that the bacteriostasis rate is improved.
The coptis chinensis extract is obtained according to the following method:
1) cleaning Coptidis rhizoma, cutting, and grinding into powder; adding methanol-hydrochloric acid solution for dissolving, performing ultrasonic treatment for 40min, cooling to room temperature, and filtering with 0.22 μm microporous filter paper; wherein the volume ratio of methanol to hydrochloric acid in the methanol-hydrochloric acid solution is 100: 1;
2) using Ca (OH)2Adjusting the pH value of the filtrate obtained in the step 1) to 5, continuously stirring during the adjustment of the pH value, then filtering, filtering the filtrate, filtering the filtered filtrate through 0.22-micron microporous filter paper, adding HCl into the filtrate to adjust the pH value to 2, adding a sodium chloride solution with the mass percentage of 5% to dissolve the filtrate, refrigerating the filtrate overnight in a refrigerator, and drying a filter cake at 50 ℃; wherein the mass volume ratio of the sodium chloride in the 5% sodium chloride solution to the filtrate is 1g:10 mL.
The adopted coptis extraction method can improve the content of alkaloid in coptis, the purity can be obviously improved, the purity can reach about 90 percent, and the berberine hydrochloride can reach 100 mu g/mL-1Left and right.
The wormwood extract is obtained according to the following method:
taking 8-month middle ten-day wormwood, drying, adding boiled distilled water according to the mass-volume ratio of 1g to 5mL, adding saturated lime water under stirring to adjust the pH value to 8, heating to 100 ℃ under the pH value, keeping for 40-50 min, adjusting the pH value to 4 under the stirring condition of 80-90 ℃, standing, performing suction filtration, washing and precipitating until the washing liquor is neutral, and drying at 50 ℃ to constant weight; collecting dried substances, adding boiled distilled water according to the mass-volume ratio of 1g to 400mL, heating and boiling for 20min until the solution is clear, filtering while hot, collecting filtrate, cooling to room temperature, performing suction filtration, washing the precipitate with water until the washing solution is neutral, and drying at 60 ℃ to constant weight to obtain the wormwood extract.
The clove extract is obtained by supercritical extraction, and the supercritical extraction conditions are as follows: the temperature is 44 ℃, the pressure is 12MPa, the time is 1-2 h, and the carbon dioxide flow is 15-20L/h.
The moisture-proof paper is obtained according to the following steps:
pulping plant fibers, then adding the pulped plant fibers into water to obtain a plant cellulose solution with the mass percent of 5%, adding schisandra chinensis nanocellulose into the water to obtain a schisandra chinensis nanocellulose solution with the mass percent of 5%, mixing the schisandra chinensis nanocellulose solution with the mass percent of 5% with the plant cellulose solution with the mass percent of 5% according to the volume ratio of 1:5, and carrying out hot-pressing drying to obtain composite paper;
step two, mixing butanetetracarboxylic acid, triethanolamine and deionized water to obtain a mixed solution of the butanetetracarboxylic acid and the triethanolamine, then soaking the composite paper into the mixed solution of the butanetetracarboxylic acid and the triethanolamine for 15min, and drying the soaked composite paper to obtain modified composite paper;
the molar ratio of the butane tetracarboxylic acid to the deionized water is 1: 40; the molar ratio of the butane tetracarboxylic acid to the triethanolamine is 1: 3;
step three, dropwise adding a sulfuric acid solution with the concentration of 5mol/L into a sodium silicate solution with the concentration of 1mol/L until the pH value is 3, then adjusting the pH value to be neutral, filtering to obtain silicon dioxide, adding the silicon dioxide into ethanol for dispersion, and then adding KH550 to obtain a modified silicon dioxide solution;
the mass ratio of the mol of the sodium silicate in the sodium silicate solution to the KH550 is 1mol:5 g;
step four, spraying the modified silicon dioxide solution on one side of the modified composite paper to obtain the moisture-proof paper;
the schisandra chinensis nanocellulose in the step one is prepared by the following steps: putting the schisandra chinensis rhizome powder into a sodium hypochlorite solution with the concentration of 1 wt%, adjusting the pH to 4 by adopting glacial acetic acid, and carrying out heating reflux reaction for 5 hours to obtain a primary reaction product; the volume ratio of the mass of the schisandra chinensis rhizome powder to a sodium hypochlorite solution with the concentration of 1 wt% is 3g:14 mL; the schisandra chinensis rhizome powder is obtained by drying schisandra chinensis rhizomes until the water content is lower than 10%, and then crushing to obtain particles with the particle size of 200-300 meshes; secondly, performing suction filtration on the primary reaction product, washing with deionized water until the filtrate obtained by suction filtration is neutral to obtain a solid product, then putting the solid yield into a sodium sulfite solution with the concentration of 8 wt%, and performing heating reflux reaction for 6 hours to obtain a secondary reaction product; the volume ratio of the mass of the solid product to the sodium sulfite solution with the concentration of 8 wt% is 1.5g:11 mL; thirdly, performing suction filtration on the secondary reaction product, washing the secondary reaction product for 3 times by using deionized water to obtain a washed solid product, putting the washed solid product into a NaOH aqueous solution with the mass fraction of 20%, stirring and reacting the solid product for 60min at the temperature of 80 ℃, and performing centrifugal separation to obtain the schisandra chinensis nanocellulose; the volume ratio of the mass of the washed solid product to the NaOH aqueous solution with the mass fraction of 20% is 1g:22 mL; the plant fiber in the step one is hardwood dissolving pulp with lignin and hemicellulose removed.
And in the second step, drying the impregnated composite paper at the temperature of 50 ℃ for 15min, and then drying at the temperature of 80 ℃ for 3 min.
And in the fourth step, spraying the modified silicon dioxide solution on one side of the modified composite paper by using a spray gun under the conditions that the distance between the spray gun and the modified composite paper is 15cm and the spraying pressure is 0.2MPa until the spraying thickness is 2 microns.
Comparative example 1
This example differs from example 1 in that the extract of green husk of walnut was omitted.
Comparative example 2
This example differs from example 1 in that the coptis extract is omitted.
Comparative example 3
This example differs from example 1 in that the wormwood extract and clove extract are omitted.
The blank control was a conventional corrugated box.
Example one moisture barrier paper was prepared having a contact angle with water of 159 °.
Experiment 1
Dissolving 45mg of walnut green husk antibacterial agent prepared in example 1 in 100mL of water to prepare an aqueous solution, and spraying the aqueous solution on the surface of corrugated medium paper 3 and the inner surface of surface paper 4 of a corrugated box, wherein the spraying amount is guaranteed to be 10g/m2And then molding, and adhering the side of the moisture-proof paper which is not subjected to hydrophobic modification to the outer surface of the surface paper 4 of the corrugated box.
The puncture strength can reach 24.3J according to GB-T6544-2008, the burst strength can reach 3095kPa according to GB-T6544-2008, and the edge pressure strength can reach 41.2kN/m according to GB-T16717.
According to the standard of GB/T4768-; after 28 days of the mildew resistance test, the results are as follows:
note: and indicate significant differences at the 0.01 and 0.05 levels, respectively, and the above bacteriostasis was averaged over three experiments.
Experiment 2
By adopting the same scheme as the experiment 1, the bacteriostasis rate is not obviously reduced after 50 days of mildew-proof tests,
from this, it can be seen that the corrugated box obtained by the scheme of example 1 can improve the bacteriostatic time.
Claims (6)
1. An antibacterial and moistureproof carton for storing fruits and fresh fruits is characterized in that the carton is a corrugated carton, and the corrugated carton comprises inner paper (1), a first buffer layer (2-1), a second buffer layer (2-2), corrugated medium paper (3) and surface paper (4) from inside to outside in sequence; the first buffer layer (2-1) and the second buffer layer (2-2) are formed by closely arranging a plurality of rows of arches, the arch of the first buffer layer (2-1) is opposite to the arch opening direction of the second buffer layer (2-2), and the arch surfaces are attached in a staggered manner; the corrugated medium paper (3) is composed of a plurality of closely arranged prismatic tables (3-2) arranged on a bottom plate (3-1), and the upper bottom surfaces of the prismatic tables (3-2) are attached to the surface paper (4); the moisture-proof paper is adhered to the outer surface of the surface paper (4) of the corrugated box, and the walnut green husk antibacterial agent is sprayed on the surface of the corrugated medium paper (3) and the inner surface of the surface paper (4) of the corrugated box;
the walnut green husk antibacterial agent consists of 8-20 parts by weight of walnut green husk extract, 5-15 parts by weight of coptis chinensis extract, 2-10 parts by weight of wormwood extract and 1-8 parts by weight of clove extract;
the walnut green husk extract is obtained according to the following method:
drying walnut green seedcases to constant weight, crushing and sieving the dried walnut green cases by a sieve of 80-100 meshes, uniformly mixing the sieved walnut green cases with ethanol according to the liquid-material ratio of 20-25 mg to 1mL to obtain a mixed solution, then adding sodium hexametaphosphate in an amount which is 0.8-1.2 times the volume of the mixed solution, uniformly mixing, and extracting for 120min at the temperature of 70 ℃ and the microwave power of 700-750W, wherein the volume percentage content of the ethanol is 50%, and the concentration of the extract is 15-25 mg/mL;
the moisture-proof paper is obtained according to the following steps:
pulping plant fibers, then adding the pulped plant fibers into water to obtain a plant cellulose solution with the mass percent of 4% -5%, adding schisandra chinensis nanocellulose into the water to obtain a schisandra chinensis nanocellulose solution with the mass percent of 4% -5%, mixing the schisandra chinensis nanocellulose solution with the mass percent of 4% -5% with the plant cellulose solution with the mass percent of 4% -5% according to the volume ratio of 1:5, and carrying out hot-pressing drying to obtain composite paper;
step two, mixing butanetetracarboxylic acid, triethanolamine and deionized water to obtain a mixed solution of the butanetetracarboxylic acid and the triethanolamine, then soaking the composite paper into the mixed solution of the butanetetracarboxylic acid and the triethanolamine for 10-20 min, and drying the soaked composite paper to obtain modified composite paper;
the molar ratio of the butane tetracarboxylic acid to the deionized water is 1 (30-50); the molar ratio of the butane tetracarboxylic acid to the triethanolamine is 1 (1-5);
step three, dropwise adding a sulfuric acid solution with the concentration of 4-6 mol/L into a sodium silicate solution with the concentration of 1-2 mol/L until the pH value is 2-4, then adjusting the pH value to be neutral, filtering to obtain silicon dioxide, adding the silicon dioxide into ethanol for dispersing, and then adding KH550 to obtain a modified silicon dioxide solution;
the mass ratio of the mol of the sodium silicate in the sodium silicate solution to the KH550 is 1mol (3-7) g;
step four, spraying the modified silicon dioxide solution on one side of the modified composite paper to obtain the moisture-proof paper;
the coptis chinensis extract is obtained according to the following steps:
1) cleaning Coptidis rhizoma, cutting, and grinding into powder; adding methanol-hydrochloric acid solution for dissolving, carrying out ultrasonic treatment for 30-40 min, cooling to room temperature, and filtering with a 0.22 mu m microporous filter membrane; wherein the volume ratio of methanol to hydrochloric acid in the methanol-hydrochloric acid solution is 100: 1;
2) using Ca (OH)2Adjusting the pH value of the filtrate obtained in the step 1) to 5-6, continuously stirring during the adjustment of the pH value, then filtering, filtering the filtrate, passing the filtered filtrate through a 0.22 mu m microporous filter membrane, adding HCl into the filtrate to adjust the pH value to 1-2, adding a sodium chloride solution with the mass percent of 5% to dissolve the filtrate, refrigerating the filtrate overnight in a refrigerator, and drying a filter cake at 50 ℃; wherein the mass volume ratio of sodium chloride in the 5% sodium chloride solution to the filtrate is 1g:10 mL;
the bacteria inhibited by the walnut green husk antibacterial agent are staphylococcus aureus, escherichia coli, bacillus subtilis, candida albicans and aspergillus;
the wormwood extract is obtained according to the following steps:
taking 8-month middle ten-day wormwood, drying, adding boiled distilled water according to the mass-volume ratio of 1g: 5-6 mL, adding saturated lime water under stirring to adjust the pH value to 8-9, heating to 100 ℃ under the pH value, keeping for 40-50 min, adjusting the pH value to 4-5 under the stirring condition of 80-90 ℃, standing, performing suction filtration, washing and precipitating until the washing liquor is neutral, and drying at 50-60 ℃ to constant weight; collecting dried substances, adding boiled distilled water according to the mass-to-volume ratio of 1g: 400-500 mL, heating, boiling and keeping for 20min until the solution is clear, filtering while hot, collecting filtrate, cooling to room temperature, performing suction filtration, washing the precipitate with water until the washing solution is neutral, and drying at 50-60 ℃ to constant weight to obtain an wormwood extract;
the clove extract is obtained by supercritical extraction, and the supercritical extraction conditions are as follows: the temperature is 44 ℃, the pressure is 12MPa, the time is 1-2 h, and the carbon dioxide flow is 15-20L/h.
2. The antibacterial and moisture-proof carton for storing fruits and fresh fruits as claimed in claim 1, wherein the walnut green husk antibacterial agent is composed of 8-15 parts by weight of walnut green husk extract, 5-10 parts by weight of coptis chinensis extract, 2-8 parts by weight of wormwood extract and 1-5 parts by weight of clove extract.
3. The antibacterial and moisture-proof carton for storing fruits and fresh fruits as claimed in claim 1, wherein the fructus Schisandrae chinensis nanocellulose in the first step is prepared by the following steps: putting the schisandra chinensis rhizome powder into a sodium hypochlorite solution with the concentration of 0.5-1 wt%, adjusting the pH to 4-5 by adopting glacial acetic acid, and carrying out heating reflux reaction for 4-6 h to obtain a primary reaction product; the volume ratio of the mass of the schisandra chinensis rhizome powder to the sodium hypochlorite solution with the concentration of 0.5-1 wt% is 3g (10-30) mL; the schisandra chinensis root and stem powder is obtained by drying schisandra chinensis roots and stems until the water content is lower than 10%, and then crushing the dried schisandra chinensis roots and stems to obtain schisandra chinensis root and stem powder with the particle size of 200-300 meshes; secondly, performing suction filtration on the primary reaction product, washing with deionized water until the filtrate obtained by suction filtration is neutral to obtain a solid product, then putting the solid product into a sodium sulfite solution with the concentration of 5-10 wt%, and performing heating reflux reaction for 4-6 h to obtain a secondary reaction product; the volume ratio of the mass of the solid product to the sodium sulfite solution with the concentration of 5-10 wt% is 1.5g (4-20) mL; thirdly, performing suction filtration on the secondary reaction product, washing the secondary reaction product for 1-3 times by using deionized water to obtain a washed solid product, placing the washed solid product into a NaOH aqueous solution with the mass fraction of 5-30%, stirring and reacting the solid product for 30-90 min at the temperature of 40-100 ℃, and performing centrifugal separation to obtain the schisandra chinensis nanocellulose; the volume ratio of the mass of the washed solid product to the NaOH aqueous solution with the mass fraction of 5-30% is 1g (10-30) mL.
4. The antibacterial moisture-proof carton for storing fruits and fresh fruits according to claim 1, wherein the plant fiber in the first step is hardwood dissolving pulp of delignification and hemicellulose.
5. The antibacterial and moisture-proof carton for storing fruits and fresh fruits according to claim 1, wherein in the second step, the impregnated composite paper is dried at a temperature of 40-60 ℃ for 10-20 min and then at a temperature of 80-100 ℃ for 2-5 min.
6. The antibacterial and moisture-proof carton for storing fruits and fresh fruits according to claim 1, wherein the modified silica solution is sprayed on one side of the modified composite paper by using a spray gun in the fourth step under the conditions that the distance between the spray gun and the modified composite paper is 15 cm-20 cm and the spraying pressure is 0.2MPa until the spraying thickness is 1 micron-3 microns.
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