CN106283923A - A kind of appendix has mildew-proof wallpaper of medicine carrying chitosan and preparation method thereof - Google Patents

A kind of appendix has mildew-proof wallpaper of medicine carrying chitosan and preparation method thereof Download PDF

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Publication number
CN106283923A
CN106283923A CN201610822670.0A CN201610822670A CN106283923A CN 106283923 A CN106283923 A CN 106283923A CN 201610822670 A CN201610822670 A CN 201610822670A CN 106283923 A CN106283923 A CN 106283923A
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chitosan
wallpaper
mildew
antimildew
medicine carrying
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CN201610822670.0A
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CN106283923B (en
Inventor
陈礼辉
林辉
黄六莲
曹石林
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Fujian Agriculture and Forestry University
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Fujian Agriculture and Forestry University
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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
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/64—Inorganic compounds
    • 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
    • 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
    • D21H21/50—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 form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The present invention discloses a kind of appendix mildew-proof wallpaper having medicine carrying chitosan and preparation method thereof, described mildew-proof wallpaper is using chitosan/glacial acetic acid mixed solution as carrier, using tripolyphosphate sodium water solution as cross-linking agent, ionic cross-linking and antimildew and antibacterial agent aqueous solution is used to prepare medicine carrying chitosan microball emulsion, and it is sprayed on the base paper surface of PVC wallpaper with Plant fiber's body paper as base material, prepare all kinds of medicine carrying chitosan/PVC mildew-proof wallpaper after drying.Mildew-proof wallpaper prepared by the present invention reaches 0 grade standard of GB (GB/T 24,346 2009), and anti-mold effect is splendid.The present invention uses ionic cross-linking to be mixed to prepare medicine carrying chitosan microball emulsion, it is not necessary to introduces organic solvent, and then makes the mildew-proof wallpaper environmental protection of preparation, safety.

Description

A kind of appendix has mildew-proof wallpaper of medicine carrying chitosan and preparation method thereof
Technical field
The present invention relates to wallpaper field, have the mildew-proof wallpaper of medicine carrying chitosan particularly to a kind of medicine carrying chitosan and appendix And preparation method thereof.
Background technology
In use, body of wall easily gets damp common wallpaper so that wallpaper adhesive and Plant fiber's substrate can not keep Being dried, constructing in addition, gluing is blocked up also makes glue be difficult to be dried, and easily grows the mycetes such as aspergillus niger, causes wallpaper in use process Mouldy raw bacterium, harm habitant's is healthy.After wallpaper is mouldy, fungal spore fills the air in atmosphere, and fungal spore passes through People breathe air and are directly entered human body, and during human contact's wallpaper, fungal spore also can enter body by the wound of skin surface In body so that health causes serious harm.Modern medicine study shows, many generations planting respiratory disease just because of Causing for human body touches fungal spore, some mycetes can also cause Fungal Skin Infection sick.Main Bacteria in air Belonging to and have Penicillium, cladosporium and aspergillus etc., they are to cause the anaphylactoid cause of disease of people's respiratory.Aspergillus is to cause spy The dangerous spores of different reaction, the respiratory symptom of child such as: asthma, pant etc. all manifests with the concentration of aspergillosis in room air Write positive correlation.
Mold proof product specifically includes that textile mildew-resistant, wrapping paper mildew-resistant, wood mould, coating for wall surface mildew-resistant etc. at present, by Later in wallpaper industry commercial production ratio, wallpaper in the market also has mildew-resistant in the case of being provided simultaneously with antibacterial and deodouring Performance little, it is therefore necessary to develop a kind of environment-friendly type antibiotic mildew-proof wallpaper.
Chitosan is the natural polymers that in nature, content is only second to cellulose, is the acetylizad product of chitin Thing, has the advantages such as nontoxic, biocompatibility and biological degradability.Chitosan surface there is also amino, at acid medium Under, the H that amino is easy with free+In conjunction with forming NH3 +, therefore chitosan is also the natural polymer that a few surface is positively charged.
Chitosan is also a kind of natural antibacterial agent, all has gram negative bacteria and gram positive bacteria good antibacterial Performance.At present, during the mildew-resistant also not having people that chitosan is applied to wallpaper processes.
Summary of the invention
For solving the problem of above-mentioned existing wallpaper anti-mold effect difference, the present invention proposes a kind of medicine carrying chitosan and appendix has load Mildew-proof wallpaper of medicine chitosan and preparation method thereof.
To this end, inventor provide following technical scheme:
A kind of preparation method of medicine carrying chitosan, described preparation method comprises the following steps:
Configuration concentration be 2～3g/L tripolyphosphate sodium water solutions as cross-linking agent, and configuration concentration is 0.5～3g/L mildew-resistant Antibacterial aqueous solution；
Chitosan is added 0.5～2% glacial acetic acid solution in, fully dissolve, and to regulate solution ph be 2～4, configuration Obtain chitosan/glacial acetic acid mixed solution that chitosan concentration is 4～16g/L as appendix agent；
Antimildew and antibacterial agent aqueous solution and cross-linking agent 1～2:1 are mixed homogeneously by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 2～4h, until Mixed solution presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution with The volume ratio of chitosan/glacial acetic acid solution is 1:1～1.5.
The present invention selects chitosan (CS) as the carrier of antimildew and antibacterial agent, is because that it is nontoxic, and drug loading is high, stays Rate of is high, the medicine carrying chitosan antimildew and antibacterial prepared functional.Using tripolyphosphate sodium water solution as cross-linking agent, select It is owing to being not related to organic solvent in ionic cross-linking preparation process that ionic cross-linking prepares medicine carrying chitosan, therefore to addition Pharmaceutical properties will not produce large effect to human body.
Before making the present invention, after also not having people that antimildew and antibacterial agent and chitosan are prepared by mixing into medicine carrying chitosan more attached It is downloaded in PVC wallpaper.The present invention innovatively by after on medicine carrying chitosan appendix to PVC wallpaper, antimildew and antibacterial agent and chitosan Synergy, make the anti-mold effect of PVC wallpaper not only substantially exceed the effect of independent loading chitosan, but also substantially exceed The individually effect of appendix antimildew and antibacterial agent.
Preferably, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is one of the following: sodium fluoride, fluorination Copper, copper sulfate, Copper hydrate, zinc chloride or sorbic acid.The present invention selects sodium fluoride (NaF), copper fluoride (CuF2), copper sulfate (CuSO4), Copper hydrate (Cu (OH)2), zinc chloride (ZnCl2) or sorbic acid (SA) etc. as antimildew and antibacterial agent, be due to these The antimildew and antibacterial performance of antimildew and antibacterial agent is good, cheap, relatively low to the toxicity of human body.Wherein, described antimildew and antibacterial agent is preferred For sodium fluoride.
Owing to the concentration of antimildew and antibacterial agent aqueous solution and chitosan/glacial acetic acid mixed solution can affect antibacterial effect.So, In the present invention, the concentration of described antimildew and antibacterial agent aqueous solution is preferably 3g/L, described chitosan/glacial acetic acid mixed solution dense Degree is preferably 16g/L.
The present invention also provides for the preparation method that a kind of appendix has the mildew-proof wallpaper of medicine carrying chitosan, described mildew-proof wallpaper be with Plant fiber's body paper is the PVC wallpaper of base material, and described preparation method comprises the following steps:
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 0.5～4mL/m2；
PVC wallpaper after spraying is dried 45～60s at 150～180 DEG C, prepares the anti-of appendix medicine carrying chitosan Mould wallpaper.
Preferably, described antimildew and antibacterial agent is one of the following: sodium fluoride, copper fluoride, copper sulfate, Copper hydrate, chlorine Change zinc or sorbic acid.
Preferably, described medicine carrying chitosan microball emulsion quantity for spray in PVC wallpaper is 2～3mL/m2。
Preferably, it is front 100～120 that the preparation method of described mildew-proof wallpaper further comprises the steps of: the spraying of described PVC wallpaper 60～90s it are dried at DEG C.By this step, remove each bacterioid carried on wallpaper and mycete in advance.
The present invention also provides for a kind of appendix the mildew-proof wallpaper of medicine carrying chitosan, and it includes PVC wallpaper layer, described PVC wall Ply of paper is the PVC wallpaper with Plant fiber's body paper as base material, and described mildew-proof wallpaper also includes the Plant fiber being coated in PVC wallpaper Medicine carrying chitosan layer on raw base paper face, the medicine carrying chitosan in described medicine carrying chitosan layer is prepared by said method.
Preferably, described medicine carrying chitosan layer is former to the Plant fiber of PVC wallpaper by medicine carrying chitosan microball Emulsion Spraying Being formed on paper substrate face, described medicine carrying chitosan microball emulsion quantity for spray in PVC wallpaper is 0.5～4mL/m2。
The invention have the benefit that
1, after the present invention is mixed with chitosan/glacial acetic acid solution by antimildew and antibacterial agent aqueous solution, medicine carrying chitosan is formed, then By on medicine carrying chitosan appendix to PVC wallpaper so that PVC wallpaper has anti-mold effect.Meanwhile, the cost of material that the present invention uses Cheap, production technology is simple, is suitable for producing in enormous quantities.
2, the medicine carrying chitosan of the present invention is using tripolyphosphate sodium water solution as cross-linking agent, uses ionic cross-linking mixing system Obtain medicine carrying chitosan microball emulsion, it is not necessary to introduce organic solvent, the not only environmental protection of the PVC wallpaper of preparation, and there is anti-mold effect.
3, showing according to detection data, the mildew-proof wallpaper mildew-resistant grade of appendix medicine carrying chitosan prepared by the present invention can reach 0 grade standard of " evaluation of textile fungicidal properties " GB (GB/T 24346-2009), anti-mold effect is splendid.
4, the present invention carries out mildew-resistant modification to PVC wallpaper, will not reduce the mechanical property of PVC wallpaper too much, and it is horizontal, vertical Remain to meet the requirement of industry standard high-class product to wet tensile (strength).
Accompanying drawing explanation
Fig. 1 is the mildew situation after inoculated aspergillus niger 20d of the mildew-proof wallpaper containing different antimildew and antibacterial agents；Wherein, (A) Reagent without mildew-resistant；(B) chitosan/copper sulfate；(C) chitosan/zinc chloride；(D) chitosan/Copper hydrate；(E) chitosan/fluorine Change copper；(F) chitosan/sorbic acid；(G) chitosan/sodium fluoride；
Fig. 2 is all kinds of wallpaper mildew situation after inoculated aspergillus niger 20d；Wherein, (A) is without mildew-resistant reagent；(B) shell gathers Sugar；(C) sodium fluoride；(D) chitosan/sodium fluoride
Fig. 3 is chitosan/sodium fluoride mildew-proof wallpaper mildew after inoculated aspergillus niger 20d prepared by different chitosan concentration Situation；Wherein, (a) is without mildew-resistant reagent；(b) 4g/L chitosan；(c) 6g/L chitosan；(d) 8g/L chitosan；(e) 10g/L shell Polysaccharide；(f) 12g/L chitosan；(g) 14g/L chitosan；(h) 16g/L chitosan
Fig. 4 is chitosan/sodium fluoride/PVC mildew-proof wallpaper mildew situation after inoculated aspergillus niger 20d；
Fig. 5 is the projection Electronic Speculum figure of chitosan/sodium fluoride microsphere；
Fig. 6 is the grain size distribution of chitosan/sodium fluoride microsphere；
Fig. 7 is the infrared spectrogram of chitosan/sodium fluoride (CS/NaF) microsphere and chitosan (CS).
Detailed description of the invention
By describing the technology contents of technical scheme, structural feature in detail, being realized purpose and effect, below in conjunction with concrete real Execute example and coordinate accompanying drawing to be explained in detail.
The present invention provides the preparation method of a kind of medicine carrying chitosan, and described preparation method comprises the following steps:
Configuration concentration be 2～3g/L tripolyphosphate sodium water solutions as cross-linking agent, and configuration concentration is 0.5～3g/L mildew-resistant Antibacterial aqueous solution；
Chitosan is added 0.5～2% glacial acetic acid solution in, fully dissolve, and to regulate solution ph be 2～4, configuration Obtain chitosan/glacial acetic acid mixed solution that chitosan concentration is 4～16g/L as appendix agent；
Antimildew and antibacterial agent aqueous solution and cross-linking agent 1～2:1 are mixed homogeneously by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 2～4h, until Mixed solution presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution with The volume ratio of chitosan/glacial acetic acid solution is 1:1～1.5.
The present invention selects chitosan (CS) as the carrier of antimildew and antibacterial agent, is because that it is nontoxic, and drug loading is high, stays Rate of is high, the medicine carrying chitosan antimildew and antibacterial prepared functional.Select ionic cross-linking prepare medicine carrying chitosan be by In ionic cross-linking preparation process, it is not related to organic solvent, therefore human body will not be produced bigger by the pharmaceutical properties added Impact.
In certain embodiments, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is one of the following: fluorination Sodium, copper fluoride, copper sulfate, Copper hydrate, zinc chloride or sorbic acid.The present invention selects sodium fluoride (NaF), copper fluoride (CuF2)、 Copper sulfate (CuSO4), Copper hydrate (Cu (OH)2), zinc chloride (ZnCl2) or sorbic acid (SA) etc. as antimildew and antibacterial agent, be by Antimildew and antibacterial performance in these antimildew and antibacterial agents is good, cheap, relatively low to the toxicity of human body.Wherein, described antimildew and antibacterial Agent is preferably sodium fluoride.
Owing to the concentration of antimildew and antibacterial agent aqueous solution and chitosan/glacial acetic acid mixed solution can affect antibacterial effect.So, In the present invention, the concentration of described antimildew and antibacterial agent aqueous solution is preferably 3g/L, described chitosan/glacial acetic acid mixed solution dense Degree is preferably 16g/L.
The present invention also provides for the preparation method that a kind of appendix has the mildew-proof wallpaper of medicine carrying chitosan, described mildew-proof wallpaper be with Plant fiber's body paper is the PVC wallpaper of base material, and described preparation method comprises the following steps:
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 0.5～4mL/m2；
PVC wallpaper after spraying is dried 45～60s at 150～180 DEG C, prepares the anti-of appendix medicine carrying chitosan Mould wallpaper.
In certain embodiments, described antimildew and antibacterial agent is one of the following: sodium fluoride, copper fluoride, copper sulfate, hydrogen-oxygen Change copper, zinc chloride or sorbic acid.
In certain embodiments, described medicine carrying chitosan microball emulsion quantity for spray in PVC wallpaper is 2～3mL/m2。
In certain embodiments, before the preparation method of described mildew-proof wallpaper further comprises the steps of: the spraying of described PVC wallpaper 60～90s it are dried at 100～120 DEG C.By this step, remove each bacterioid carried on wallpaper and mycete in advance.
The present invention also provides for a kind of appendix the mildew-proof wallpaper of medicine carrying chitosan, and it includes PVC wallpaper layer, described PVC wall Ply of paper is the PVC wallpaper with Plant fiber's body paper as base material, and described mildew-proof wallpaper also includes the Plant fiber being coated in PVC wallpaper Medicine carrying chitosan layer on raw base paper face, the medicine carrying chitosan in described medicine carrying chitosan layer is prepared by said method.
In certain embodiments, described medicine carrying chitosan layer is by medicine carrying chitosan microball Emulsion Spraying planting to PVC wallpaper Being formed on fibres raw base paper face, described medicine carrying chitosan microball emulsion quantity for spray in PVC wallpaper is 0.5～4mL/ m2。
Specific embodiment prepared by mildew-proof wallpaper
Embodiment 1
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 3g/L antimildew and antibacterial agent water Solution；Antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 0.5%, fully dissolve, and to regulate solution ph be 2, configuration obtains shell Glycan concentration is that the chitosan/glacial acetic acid mixed solution of 6g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1:1 by volume, obtains antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 2h, until mixing molten Liquid presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution gathers with shell The volume ratio of sugar/glacial acetic acid solution is 1:1.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 100 DEG C, be dried 90s in advance, remove in PVC wallpaper Various antibacterials and mycete；
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 0.5mL/m2；
PVC wallpaper after spraying is dried 60s at 150 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 2
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 3g/L antimildew and antibacterial agent water Solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is copper fluoride.
Being added by chitosan in the glacial acetic acid solution of 0.5%, fully dissolve, and to regulate solution ph be 2, configuration obtains shell Glycan concentration is that the chitosan/glacial acetic acid mixed solution of 6g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1:1 by volume, obtains antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 2h, until mixing molten Liquid presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution gathers with shell The volume ratio of sugar/glacial acetic acid solution is 1:1.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 100 DEG C, be dried 90s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 4mL/m2；
PVC wallpaper after spraying is dried 60s at 150 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 3
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 3g/L antimildew and antibacterial agent water Solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is copper sulfate.
Being added by chitosan in the glacial acetic acid solution of 0.1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell Glycan concentration is that the chitosan/glacial acetic acid mixed solution of 6g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1:1 by volume, obtains antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixing molten Liquid presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution gathers with shell The volume ratio of sugar/glacial acetic acid solution is 1:1.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 100 DEG C, be dried 90s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 4mL/m2；
PVC wallpaper after spraying is dried 45s at 180 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 4
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 3g/L antimildew and antibacterial agent water Solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is Copper hydrate.
Being added by chitosan in the glacial acetic acid solution of 0.1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell Glycan concentration is that the chitosan/glacial acetic acid mixed solution of 6g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1:1 by volume, obtains antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixing molten Liquid presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution gathers with shell The volume ratio of sugar/glacial acetic acid solution is 1:1.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 120 DEG C, be dried 60s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 3mL/m2；
PVC wallpaper after spraying is dried 45s at 180 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 5
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 3g/L antimildew and antibacterial agent water Solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is zinc chloride.
Being added by chitosan in the glacial acetic acid solution of 2%, fully dissolve, and to regulate solution ph be 4, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 6g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1:1 by volume, obtains antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 4h, until mixing molten Liquid presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution gathers with shell The volume ratio of sugar/glacial acetic acid solution is 1:1.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 120 DEG C, be dried 60s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 3mL/m2；
PVC wallpaper after spraying is dried 55s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 6
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 3g/L antimildew and antibacterial agent water Solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sorbic acid.
Being added by chitosan in the glacial acetic acid solution of 2%, fully dissolve, and to regulate solution ph be 4, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 6g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1:1 by volume, obtains antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 4h, until mixing molten Liquid presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution gathers with shell The volume ratio of sugar/glacial acetic acid solution is 1:1.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 120 DEG C, be dried 60s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 170 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 7
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 3g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 0.5g/L antimildew and antibacterial agent Aqueous solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 4g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1.5:1 by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixed Close solution and present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and shell The volume ratio of polysaccharide/glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 120 DEG C, be dried 60s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 8
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 0.5g/L antimildew and antibacterial agent Aqueous solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 6g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1.5:1 by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixed Close solution and present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and shell The volume ratio of polysaccharide/glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 120 DEG C, be dried 60s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 9
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 0.5g/L antimildew and antibacterial agent Aqueous solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 8g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 2:1 by volume, obtains antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixing molten Liquid presents shallow white, stops stirring, obtains medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution gathers with shell The volume ratio of sugar/glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 80s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 10
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 0.5g/L antimildew and antibacterial agent Aqueous solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 10g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent by volume 2:1, obtains antimildew and antibacterial agent mixed solution, so After antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, be stirred at room temperature 3h, until mixed solution Present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and chitosan/ The volume ratio of glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 70s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 11
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 0.5g/L antimildew and antibacterial agent Aqueous solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 12g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1.5:1 by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixed Close solution and present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and shell The volume ratio of polysaccharide/glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 80s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 12
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 0.5g/L antimildew and antibacterial agent Aqueous solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 14g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1.5:1 by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixed Close solution and present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and shell The volume ratio of polysaccharide/glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 80s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 13
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 0.5g/L antimildew and antibacterial agent Aqueous solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 16g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1.5:1 by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixed Close solution and present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and shell The volume ratio of polysaccharide/glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 80s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 14 (with reference to embodiment)
Prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 80s in advance, remove in PVC wallpaper Various antibacterials and mycete.
The chitosan microball emulsion (chitosan concentration is 16g/L) not containing antimildew and antibacterial agent is sprayed to PVC wallpaper In the one side of Plant fiber's body paper base material, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 45～60s at 150～180 DEG C, prepares the anti-of appendix medicine carrying chitosan Mould wallpaper.
Embodiment 15 (with reference to embodiment)
Prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 80s in advance, remove in PVC wallpaper Various antibacterials and mycete.
The sodium fluoride aqueous solution that concentration is 3g/L is sprayed in the one side of Plant fiber's body paper base material of PVC wallpaper, spray The emulsion amount being coated with is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
Embodiment 16
1, first preparing medicine carrying chitosan, it comprises the following steps:
Configuration concentration be 2g/L tripolyphosphate sodium water solution as cross-linking agent, and configuration concentration is 3g/L antimildew and antibacterial agent water Solution, the antimildew and antibacterial agent in described antimildew and antibacterial agent aqueous solution is sodium fluoride.
Being added by chitosan in the glacial acetic acid solution of 1%, fully dissolve, and to regulate solution ph be 3, configuration obtains shell and gathers Sugar concentration is that the chitosan/glacial acetic acid mixed solution of 16g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution is mixed homogeneously with cross-linking agent 1.5:1 by volume, obtains antimildew and antibacterial agent mixing molten Liquid, is then slowly dropped into antimildew and antibacterial agent mixed solution in chitosan/glacial acetic acid solution, is stirred at room temperature 3h, until mixed Close solution and present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and shell The volume ratio of polysaccharide/glacial acetic acid solution is 1:1.5.
2, prepare mildew-proof wallpaper, comprise the following steps:
Select the PVC wallpaper with Plant fiber's body paper as base material, at 110 DEG C, be dried 80s in advance, remove in PVC wallpaper Various antibacterials and mycete.
By Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper In one side, the emulsion amount of spraying is 2mL/m2；
PVC wallpaper after spraying is dried 50s at 160 DEG C, prepares the mildew-proof wallpaper of appendix medicine carrying chitosan.
The various performances detection of mildew-proof wallpaper prepared by each embodiment.
First carry out the cultivation of aspergillus niger strain and the preparation of spore liquid thereof.Method particularly includes: by peeling potatoes, stripping and slicing, Put in deionized water, at 121 DEG C, boil 30min, after being cooked into pureed, go out potato starch filtrate by filtered through gauze；Filtrate Middle addition glucose, loads triangular flask, prepares potato culture solution after cooling gel after stirring.
By inoculating loop and potato culture through pressure cooker sterilizing, it is placed on the aseptic superclean bench of bio-safety, The Aspergillus niger spores purchased is seeded in potato culture inclined-plane, puts in biochemical cultivation case, at 28 DEG C cultivate 7d～ 14d, until covering with mycotic spore on potato culture inclined-plane.
Measure 10mL in autoclaved deionized water pours the potato culture inclined-plane covering with mycotic spore into, use The inoculating loop that autoclaving is crossed scrapes the surface of aspergillus niger strain lightly, makes Aspergillus niger spores be dispersed in aseptic ionized water, Become the aqueous solution containing spore；The aqueous solution containing spore washed out is poured in the triangular flask containing bead, uses constant temperature Agitator vibrates triangular flask at 28 DEG C, makes spore liquid fully be mixed；Spore liquid after mixing is filtered with qualitative filter paper, removes The impurity such as mycelia fragment, agar and spore ball, the solution after filtration is the Aspergillus niger spores liquid prepared.
Aspergillus niger inoculation on mildew-proof wallpaper and cultural method be: at potato culture, inoculating loop etc. through high pressure After steam sterilization, potato culture solution is uniformly introduced in culture dish by aseptic working platform, treat that culture medium cooling is solidifying Gu after, drawing 1mL spore liquid with the glue head straw of sterilizing, uniform distribution is inoculated into the surface of whole culture medium, uses sterilizing Glass spreading rod smear uniformly；Inoculated media surface is put into a piece of PVC wallpaper sample through sterilization processing, PVC wallpaper sample is square or the circle of diameter 40mm of length of side 40mm.After media surface moisture somewhat evaporates, lid Good culture dish lid, and seal with sealed membrane and preservative film；Every kind of PVC wallpaper sample does 3 parallel tests；Vaccinated and add The culture dish entering mildew-resistant PVC wallpaper sample is put in THE CONSTANT TEMPERATURE AND HUMIDITY BIOLOGICAL CABINET, at temperature 28 DEG C ± 2 DEG C and relative humidity 20d is cultivated under conditions of 90% ± 5%；After the cultivation of 20d, by culture medium and the length of PVC wallpaper in observation culture dish Mould situation, picks out the optimal medicine carrying chitosan of anti-mold effect/PVC mildew-proof wallpaper sample.
1, the anti-mold effect of different medicine carrying chitosan is investigated
Embodiment 1 prepares 6 kinds of medicine carrying chitosans containing different antimildew and antibacterial agents respectively to the first step of embodiment 6. Wherein, the concentration of described antimildew and antibacterial agent aqueous solution is 3g/L.Described antimildew and antibacterial agent is respectively sodium fluoride (NaF), fluorination Copper (CuF2), copper sulfate (CuSO4), Copper hydrate (Cu (OH)2), zinc chloride (ZnCl2) and sorbic acid (sorbic acid, letter Claim SA).By the antimildew and antibacterial agent aqueous solution that concentration is 3g/L and sodium tripolyphosphate (STPP) aqueous solution that concentration is 2g/L After, carry out cross-linking reaction with chitosan (CS)/glacial acetic acid (AC) solution that concentration is 6g/L respectively, prepare 6 kinds are different Medicine carrying chitosan microball emulsion, particularly as follows: chitosan/sodium fluoride (CS/NaF), chitosan/copper fluoride (CS/CuF2), shell gather Sugar/copper sulfate (CS/CuSO4), chitosan/Copper hydrate (CS/Cu (OH)2), chitosan/zinc chloride (CS/ZnCl2) and shell gather Sugar/sorbic acid (CS/SA).
Through the second step spray treatment of embodiment 1 to embodiment 6, obtain 6 kinds of mildew-proof wallpapers.Above-described embodiment 1 is to real Execute 6 kinds of mildew-proof wallpapers of example 6 preparation, put into aspergillus niger spore together with control sample (PVC wallpaper of non-appendix antimildew and antibacterial agent) Sub-liquid is sprawled in uniform potato culture, cultivates under conditions of temperature 28 DEG C ± 2 DEG C and relative humidity 90% ± 5% After 20d, observe mildew situation.Every kind of wallpaper is divided into 3 groups, as parallel test to get rid of error, and the test of wallpaper mildew situation Result is as shown in Figure 1.
As shown in Figure 1, embodiment 2 uses chitosan/copper fluoride (CS/CuF respectively to embodiment 62), chitosan/sulphuric acid Copper (CS/CuSO4), chitosan/Copper hydrate (CS/Cu (OH)2), chitosan/zinc chloride (CS/ZnCl2) and chitosan/Pyrusussuriensis Prepared by acid (CS/SA) goes out mildew-proof wallpaper sample B, sample C, sample D, sample E and sample F, cultivates in Aspergillus niger spores liquid Mildew situation after 20d, the PVC wallpaper control sample A all with without antifungus agent is similar, illustrates that embodiment 2 is prepared to embodiment 6 Medicine carrying chitosan poor to the anti-mold effect of aspergillus niger；Use chitosan/sodium fluoride (CS/ prepared by embodiment 1 first step NaF) carrying out the mildew-resistant PVC wallpaper that appendix obtains, its aspergillus niger mildew area is minimum, illustrates that chitosan/sodium fluoride is in PVC wallpaper After upper appendix, aspergillus niger is had preferable anti-mold effect.
Owing to the mildew-resistant grade of wall paper products not yet exists any country, place or industry standard, therefore push away according to country Recommend the anti-mold effect evaluation criterion about textile in standard " evaluation of textile fungicidal properties " (GB/T 24346-2009), right The anti-mold effect of aspergillus niger is evaluated by self-control mildew-proof wallpaper.The anti-mold effect evaluation of standard GB/T/T 24346-2009 Grade is as shown in table 1,
Table 1 textile anti-mold effect is evaluated
According in table 1 about the evaluation criterion of textile anti-mold effect, to above 7 groups of medicine carrying chitosan/PVC wallpaper to black The anti-mold effect of aspergillosis carries out mildew-resistant grade evaluation, and it the results are shown in Table 2.
Table 2 medicine carrying chitosan mildew-resistant grade is evaluated
As shown in table 2, embodiment 1 uses the mildew-resistant PVC wallpaper that chitosan/sodium fluoride (CS/NaF) is prepared, and it is to black The average mildew-resistant grade of aspergillosis reaches national 2 grade standards, and anti-mold effect is preferable；The average mildew-resistant grade of other medicines and blank examination The average mildew-resistant grade testing group is identical, and for national 4 grade standards, mildew-resistant area is almost nil, and anti-mold effect is very poor.So the present invention Preferably as antifungus agent, PVC wallpaper to carry out mildew-resistant modified for chitosan/sodium fluoride (CS/NaF) microsphere emulsion.
In embodiment 1 to embodiment 6, in chitosan/glacial acetic acid mixed solution, chitosan concentration is 6g/L, if by carrying High chitosan concentration, then after copper fluoride, copper sulfate, Copper hydrate, zinc chloride or sorbic acid mix with chitosan/glacial acetic acid solution It is modified that the medicine carrying chitosan of preparation can also carry out mildew-resistant to PVC wallpaper.
2, the mould proof test of chitosan/sodium fluoride system
Method particularly includes: having the PVC wallpaper of chitosan for comparison with one group of non-appendix, embodiment 14 is not for add antibacterial And the PVC wallpaper of the chitosan solution spraying that concentration is 6g/L, embodiment 15 is individually to use sodium fluoride (NaF) solution of 3g/L The PVC wallpaper of spraying, by above-mentioned three groups of PVC wallpaper with embodiment 13 with chitosan/sodium fluoride (CS/NaF) microsphere Emulsion Spraying PVC wallpaper synchronize carry out the mould proof test to aspergillus niger.Every kind of wallpaper is divided into 2 groups, as parallel test to get rid of error, wall The result of the test of paper mildew situation is as shown in Figure 2.
As seen from Figure 2, embodiment 14 use chitosan (CS) spraying preparation go out PVC wallpaper sample B, at aspergillus niger Spore liquid is cultivated the mildew situation after 20d, similar with the PVC wallpaper control sample A without antifungus agent, illustrate that chitosan is to black The anti-mold effect of aspergillosis is poor；Embodiment 15 is used alone sodium fluoride (NaF) and sprays the PVC wallpaper sample C prepared, to black fermented preparation Mould have certain anti-mold effect, and its sample the most do not finds mildew, but the mildew-resistant of sample surrounding media blank space Effect is poor, and mildew area is bigger；Embodiment 13 uses the mildew-resistant PVC wallpaper sample that chitosan/sodium fluoride (CS/NaF) is prepared Product D, its sample does not find mildew, and the aspergillus niger mildew area of sample surrounding media blank space is minimum.This illustrates to implement Aspergillus niger is not played anti-mold effect by the independent chitosan appendix wallpaper of example 14, the wallpaper of the independent sodium fluoride appendix of embodiment 15, Poor to the anti-mold effect of aspergillus niger, embodiment 13 mixed shell polysaccharide and sodium fluoride, attached after preparing chitosan/sodium fluoride microsphere It is loaded in PVC wallpaper, aspergillus niger is had preferable anti-mold effect.
According in table 1 about the evaluation criterion of textile anti-mold effect, to the mildew-resistant to aspergillus niger of the above 4 groups of PVC wallpaper Effect carries out mildew-resistant grade evaluation, and it the results are shown in Table 3.
Table 3 PVC wallpaper mildew-resistant grade is evaluated
As shown in table 3, the mildew-resistant PVC wallpaper of embodiment 13 appendix chitosan/sodium fluoride (CS/NaF), it is to aspergillus niger Average mildew-resistant grade reaches national 2 grade standards, and mildew-resistant area has reached 70%, and anti-mold effect is preferable；The independent appendix of embodiment 15 The PVC wallpaper of sodium fluoride (NaF), it reaches national 3 grade standards to the average mildew-resistant grade of aspergillus niger, and anti-mold effect is general；Real Execute the PVC wallpaper of the independent appendix chitosan (CS) of example 14, the average mildew-resistant grade phase of its average mildew-resistant grade and blank assay group With, for national 4 grade standards, mildew-resistant area is almost nil, and anti-mold effect is very poor.The above-mentioned chitosan that analysis shows is total to sodium fluoride Same-action improves the sodium fluoride anti-mold effect to aspergillus niger.
3, the chitosan concentration impact on anti-mold effect
Chitosan is as the carrier of antimildew and antibacterial agent, and anti-mold effect is had a very big impact by its concentration change.So it is real Execute example 7 and prepare chitosan/sodium fluoride (CS/NaF) microsphere emulsion appendix to PVC wallpaper to embodiment 13 with different chitosan concentrations On, and detect the anti-mold effect of PVC mildew-proof wallpaper prepared by each embodiment.
Meanwhile, with the PVC wallpaper of non-appendix chitosan/sodium fluoride (CS/NaF) microsphere emulsion as control sample, together Carry out the mould proof test to aspergillus niger.The anti-mold effect of aspergillus niger is shown in by PVC mildew-proof wallpaper prepared by the chitosan of variable concentrations Fig. 3.
As seen from Figure 3, embodiment 7 uses the chitosan (CS) of variable concentrations to prepare chitosan/fluorine to embodiment 13 Changing sodium (CS/NaF)/PVC mildew-proof wallpaper, after inoculated aspergillus niger 20d, the mildew area of aspergillus niger is along with the increasing of chitosan concentration Add and constantly reduce.When the chitosan using embodiment 7 to be followed successively by 4g/L, 6g/L, 8g/L and 10g/L to embodiment 10 concentration is molten Chitosan/sodium fluoride that liquid is prepared/PVC mildew-proof wallpaper sample b, sample c, sample d and sample e, in Aspergillus niger spores liquid Cultivating the mildew situation after 20d, control sample a is similar with sodium fluoride (the NaF)/PVC wallpaper without chitosan, and this illustrates concentration The chitosan solution of≤10g/L prepares chitosan/sodium fluoride/PVC mildew-proof wallpaper, poor to the anti-mold effect of aspergillus niger；Work as reality Execute example 11 and be followed successively by, to embodiment 13 concentration, chitosan/fluorination that the chitosan solution of 12g/L, 14g/L and 16g/L is prepared Sodium/PVC mildew-proof wallpaper sample f, sample g and sample h, almost without finding mildew on its sample, sample surrounding media is blank The aspergillus niger mildew area at place is gradually reduced along with being continuously increased of chitosan solution concentration, this explanation concentration >=12g/L's Chitosan solution prepares chitosan/sodium fluoride/PVC mildew-proof wallpaper, preferable to the anti-mold effect of aspergillus niger.
According in table 1 about the evaluation criterion of textile anti-mold effect, to the mildew-resistant to aspergillus niger of the above 8 groups of PVC wallpaper Effect carries out mildew-resistant grade evaluation, and it the results are shown in Table 4.
Table 4 variable concentrations chitosan mildew-resistant grade is evaluated
From table 4, it can be seen that along with the increase of chitosan solution concentration, chitosan/sodium fluoride (CS/NaF)/PVC mildew-resistant The mildew-resistant grade evaluation effect of wallpaper sample is the best；As chitosan solution concentration≤8g/L, the chitosan/sodium fluoride prepared (CS/NaF)/PVC mildew-proof wallpaper sample, its average mildew-resistant grade is identical with the average mildew-resistant grade of blank assay group, for country 4 Grade standard, anti-mold effect is very poor；When embodiment 10 and embodiment 11 chitosan solution concentration arrive 10g/L～12g/L, sample Mildew-resistant area reach about 40%, the average mildew-resistant grade of aspergillus niger is reached national 3 grade standards；When embodiment 12 and enforcement When example 13 chitosan solution concentration reaches 14g/L～16g/L, the mildew-resistant area of sample has reached about 80%, to aspergillus niger Average mildew-resistant grade reaches national 2 grade standards, and anti-mold effect is preferable.
4, the determination of chitosan/concentration of sodium fluoride formula
The embodiment 16 chitosan/glacial acetic acid (CS/AC) mixed solution using chitosan concentration as 16g/L as carrier, with Concentration be sodium fluoride (NaF) solution of 3g/L as antimildew and antibacterial agent, the sodium tripolyphosphate (STPP) with concentration as 2g/L is water-soluble Liquid, as cross-linking agent, is mixed to prepare chitosan/sodium fluoride (CS/NaF) microsphere emulsion；By micro-for chitosan/sodium fluoride (CS/NaF) Ball Emulsion Spraying on the base paper surface of Plant fiber's paper substrate/PVC wallpaper, prepare after drying chitosan/sodium fluoride (CS/NaF)/ PVC mildew-proof wallpaper；Finally it is carried out the mould proof test of aspergillus niger.Chitosan/sodium fluoride (CS/NaF)/PVC mildew-proof wallpaper pair The anti-mold effect of aspergillus niger is shown in Fig. 4.
As seen from Figure 4, according to the experiment condition of embodiment 16, chitosan (CS) solution concentration is 16g/L, sodium fluoride (NaF) concentration of aqueous solution is chitosan/sodium fluoride (CS/NaF)/PVC mildew-proof wallpaper sample that 3g/L prepares, at inoculation black fermented preparation After mould 20d, with sample surrounding media blank space all almost without finding mildew on sample, according to textile relevant in table 1 The evaluation criterion of anti-mold effect, prevents aspergillus niger chitosan/sodium fluoride (the CS/NaF)/PVC mildew-proof wallpaper of above-mentioned preparation Mould effect carries out mildew-resistant grade evaluation, and sample is without obvious mildew under magnifier, and mildew-resistant area has nearly reached 100%, made Sample reaches national 0 grade standard to the average mildew-resistant grade of aspergillus niger, and anti-mold effect is splendid.
5, the materialization of chitosan/sodium fluoride microsphere characterizes
The morphology analysis of 5.1 chitosans/sodium fluoride microsphere
In order to confirm the morphological characteristic of chitosan/sodium fluoride (CS/NaF) microsphere, use Japan's JEOL transmission electron microscope to reality Executing chitosan/sodium fluoride microsphere form prepared by example 16 first step to observe, its result is shown in Fig. 5.
From fig. 5, it can be seen that when the concentration ratio of chitosan (CS) and sodium fluoride (NaF) is during for 16:3, chitosan (CS) and Sodium fluoride (NaF) is by compound chitosan/sodium fluoride (CS/NaF) the microsphere shape prepared of the crosslinking of sodium tripolyphosphate (STPP) Size distribution is uniform, is substantially in the form of and reveals spherical state.
In order to measure the size of chitosan/sodium fluoride (CS/NaF) microsphere, use Malvern laser particle instrument to shell The particle diameter distribution of polysaccharide/sodium fluoride microsphere measures, and its result is shown in Fig. 6.
As shown in Figure 6, when the concentration ratio of chitosan (CS) and sodium fluoride (NaF) is during for 16:3, chitosan/sodium fluoride (CS/ NaF) particle diameter of microsphere is distributed between 400nm～700nm, and mean diameter is 615nm, and chitosan/sodium fluoride (CS/NaF) is micro- Ball size distribution is uniform, and particle diameter is less, after being sprayed on the base paper surface of Plant fiber's paper substrate/PVC wallpaper, and chitosan/fluorination Sodium (CS/NaF) microsphere is liable to stick on the fiber of Plant fiber's paper substrate, makes PVC wallpaper have the effect of antimildew and antibacterial.
The infrared spectrum analysis of 5.2 chitosans/sodium fluoride microsphere
In order to measure the chemical bond change after ionic cross-linking prepares chitosan/sodium fluoride (CS/NaF) microsphere, use Fu Shell before sodium fluoride/chitosan (CS/NaF) microsphere that embodiment 16 first step is prepared by vertical leaf infrared spectrometer and preparation Polysaccharide (CS) detects, and to observe the chitosan (CS) chemical bond change before and after preparation, its result is shown in Fig. 7.
As it is shown in fig. 7, when the concentration ratio of chitosan (CS) and sodium fluoride (NaF) is during for 16:3 in embodiment 16, chitosan (CS)-OH, c h bond stretching vibration occur in 3387cm-1And 2876cm-1；Meanwhile, chitosan includes two features Absworption peak, is 1598cm respectively-1(amido link I) and 1384cm-1(amido link II).Lead to chitosan (CS) at sodium fluoride (NaF) Cross after sodium tripolyphosphate (TPP) cross-linking agent is combined with each other, the infrared spectrogram of chitosan/sodium fluoride (CS/NaF) and chitosan Comparing, its characteristic absorption peak has transferred to 1576cm-1And 1412cm-1, chitosan is at 1085cm simultaneously-1-OH the push-to at place crosses friendship Connection compound reaction is moved to 1079cm-1Place.Two infrared spectrum absorbance curve from Fig. 7 are it can be seen that chitosan/fluorination , compared with the spectrogram of chitosan (CS), there is not new characteristic peak, simply occurs in that feature in sodium (CS/NaF) spectrogram The movement at peak.This explanation sodium fluoride (NaF) and the crosslinking method that crosslinking is physical change of chitosan (CS), do not produce new Material；Sodium fluoride (NaF) and chitosan (CS) form chitosan/sodium fluoride (CS/ under the effect of sodium tripolyphosphate (TPP) NaF) microsphere；Chitosan in acid condition ,-the NH on surface2Key decomposes so that chitosan solution is with positive charge, by quiet Electro ultrafiltration is combined together to form medicine carrying chitosan with the cross-linking agent with negative charge.
6, the mechanical property of mildew-proof wallpaper
PVC wallpaper is carried out mildew-resistant modified, it is necessary to premised on not reducing its mechanical property.Shell with embodiment 16 preparation Polysaccharide/sodium fluoride (CS/NaF)/PVC mildew-proof wallpaper is sample；Carry out with the horizontal tensile testing machine of computer observing and controlling after its cutting Wet tensile (strength) must be tested.PVC wallpaper with Plant fiber's body paper as base material carries out the horizontal stroke after mildew-resistant before modified, longitudinal wet anti-tensile Intensity contrast is shown in Table 5.
As can be seen from Table 5, the PVC wall after embodiment 16 uses chitosan/sodium fluoride (CS/NaF) microsphere emulsion modified Paper, it is horizontal, longitudinal wet tensile strength reduces 2.65% and 1.74% before modified than mildew-resistant respectively.This is because the present invention uses The base material of PVC wallpaper be Plant fiber's body paper, it is quilt after coating chitosan/sodium fluoride (CS/NaF) microsphere emulsion Fully moistening.In wet conditions, the fiber in plant fiber paper there occurs that profit rises, and the many hydrogen bonds between fiber are destroyed, and causes The adhesion making paper is greatly reduced；After again drying wallpaper, the hydrogen bond of original fracture is during being again dried Can not completely recover, cause its mechanical property to decline.Although it is modified that the PVC wallpaper of the present invention carries out mildew-resistant, its horizontal stroke, Longitudinal wet tensile strength has declined, but because the range of decrease is the least, meets light industry proposed standard " wallpaper " (QB/T 4034- 2010) standard of high-class product (moistening tensile load >=0.33kN/m horizontal, longitudinal) in.
As can also be seen from Table 5, the longitudinal wet tensile strength of PVC wallpaper is all higher than horizontal wet anti-tensile the most afterwards in mildew-resistant Intensity.This is because the base material of the PVC mildew-proof wallpaper of the present invention is Plant fiber's body paper, its longitudinal wet tensile strength is the biggest In horizontal wet tensile (strength).Therefore the horizontal stroke of Plant fiber's body paper, the difference of vertical mixing coefficient determine the horizontal stroke of PVC wallpaper, indulge The difference of mechanical property.
Wet tensile (strength) after table 5 PVC wallpaper mildew-resistant before modified
In a word, the mildew-resistant modification of PVC wallpaper will not reduce the mechanical property of PVC wallpaper too much, meets light industry and pushes away Recommend the standard of high-class product in standard " wallpaper " (QB/T 4034-2010) (moistening tensile load >=0.33kN/m horizontal, longitudinal).
In sum, the invention have the advantages that
(1) present invention is using chitosan/glacial acetic acid mixed solution as carrier, using tripolyphosphate sodium water solution as crosslinking Agent, respectively using sodium fluoride, copper fluoride, copper sulfate, Copper hydrate, zinc chloride and sorbic acid as antimildew and antibacterial agent, uses ion Cross-linking method is mixed to prepare medicine carrying chitosan microball emulsion, and is sprayed on PVC wallpaper with Plant fiber's body paper as base material Base paper surface, prepares all kinds of medicine carrying chitosan/PVC mildew-proof wallpaper after drying.At chitosan solution, antimildew and antibacterial agent, trimerization The concentration ratio of sodium phosphate aqueous solution is during for 16:3:2, and chitosan/sodium fluoride/PVC mildew-proof wallpaper is to the anti-mold effect of aspergillus niger Good.
(2) present invention uses PVC wallpaper prepared by chitosan/sodium fluoride microsphere emulsion to the anti-mold effect of aspergillus niger Good.
(3) anti-mold effect of chitosan/sodium fluoride/PVC mildew-proof wallpaper is continuous along with the increase of chitosan solution concentration Promoting, when chitosan solution concentration reaches 14g/L or above, the mildew-resistant area of aspergillus niger is reached by mildew-proof wallpaper sample About 80%, the average mildew-resistant grade of aspergillus niger is reached national 2 grade standards, anti-mold effect is preferable.
(4) being 16g/L when chitosan solution concentration, Fluorinse concentration is the chitosan/fluorination prepared during 3g/L Sodium/PVC mildew-proof wallpaper, mildew-proof wallpaper has nearly reached 100% to the mildew-resistant area of aspergillus niger, the average mildew-resistant etc. to aspergillus niger Level reaches national 0 grade standard, and anti-mold effect is splendid.
(5) when the concentration ratio of chitosan and sodium fluoride is during for 16:3, observation indicate that of projection Electronic Speculum, chitosan/fluorine Change sodium microsphere shape size distribution uniform, be substantially in the form of and reveal spherical state, thus can more effectively play the mildew-resistant of sodium fluoride Effect；
(6) PVC wallpaper carrying out mildew-resistant modified, will not reduce the mechanical property of PVC wallpaper too much, it is horizontal, longitudinal wet Tensile strength remains to meet the requirement of industry standard high-class product.
It should be noted that in this article, the relational terms of such as first and second or the like is used merely to a reality Body or operation separate with another entity or operating space, and deposit between not necessarily requiring or imply these entities or operating Relation or order in any this reality.And, term " includes ", " comprising " or its any other variant are intended to Comprising of nonexcludability, so that include that the process of a series of key element, method, article or terminal unit not only include those Key element, but also include other key elements being not expressly set out, or also include for this process, method, article or end The key element that end equipment is intrinsic.In the case of there is no more restriction, statement " including ... " or " comprising ... " limit Key element, it is not excluded that there is also other key element in including the process of described key element, method, article or terminal unit.This Outward, in this article, " be more than ", " being less than ", " exceeding " etc. are interpreted as not including this number；More than " ", " below ", " within " etc. understand For including this number.
Although being described the various embodiments described above, but those skilled in the art once know basic wound The property made concept, then can make other change and amendment to these embodiments, so the foregoing is only embodiments of the invention, Not thereby the scope of patent protection of the present invention, every equivalent structure utilizing description of the invention and accompanying drawing content to be made are limited Or equivalence flow process conversion, or directly or indirectly it is used in other relevant technical fields, the most in like manner it is included in the patent of the present invention Within protection domain.

Claims (10)

1. the preparation method of a medicine carrying chitosan, it is characterised in that: described preparation method comprises the following steps:
Configuration concentration be 2～3g/L tripolyphosphate sodium water solutions as cross-linking agent, and configuration concentration is 0.5～3g/L antimildew and antibacterial Agent aqueous solution；
Chitosan is added 0.5～2% glacial acetic acid solution in, fully dissolve, and to regulate solution ph be 2～4, configuration obtains Chitosan concentration is that the chitosan/glacial acetic acid mixed solution of 4～16g/L is as appendix agent；
Antimildew and antibacterial agent aqueous solution and cross-linking agent 1～2:1 are mixed homogeneously by volume, obtain antimildew and antibacterial agent mixed solution, Then antimildew and antibacterial agent mixed solution is slowly dropped in chitosan/glacial acetic acid solution, is stirred at room temperature 2～4h, until mixed Close solution and present shallow white, stop stirring, obtain medicine carrying chitosan microball emulsion；Described antimildew and antibacterial agent mixed solution and shell The volume ratio of polysaccharide/glacial acetic acid solution is 1:1～1.5.
The preparation method of medicine carrying chitosan the most according to claim 1, it is characterised in that: described antimildew and antibacterial agent aqueous solution In antimildew and antibacterial agent be one of the following: sodium fluoride, copper fluoride, copper sulfate, Copper hydrate, zinc chloride or sorbic acid.
The preparation method of medicine carrying chitosan the most according to claim 2, it is characterised in that: described antimildew and antibacterial agent is fluorination Sodium.
The preparation method of medicine carrying chitosan the most according to claim 1, it is characterised in that: described antimildew and antibacterial agent aqueous solution Concentration be 3g/L, the concentration of described chitosan/glacial acetic acid mixed solution is 16g/L.
5. a preparation method for the mildew-proof wallpaper of the medicine carrying chitosan that appendix is had the right described in one of requirement 1-4, described mildew-resistant Wallpaper is the PVC wallpaper with Plant fiber's body paper as base material, it is characterised in that: described preparation method comprises the following steps:
One side by Plant fiber's body paper base material of the medicine carrying chitosan microball Emulsion Spraying containing antimildew and antibacterial agent to PVC wallpaper On, the emulsion amount of spraying is 0.5～4mL/m2；
PVC wallpaper after spraying is dried at 150～180 DEG C 45～60s, and preparing appendix has the mildew-resistant of medicine carrying chitosan Wallpaper.
The preparation method of mildew-proof wallpaper the most according to claim 5, it is characterised in that: described antimildew and antibacterial agent be following in One: sodium fluoride, copper fluoride, copper sulfate, Copper hydrate, zinc chloride or sorbic acid.
The preparation method of mildew-proof wallpaper the most according to claim 5, it is characterised in that: described medicine carrying chitosan microball emulsion Quantity for spray in PVC wallpaper is 2～3mL/m2。
The preparation method of mildew-proof wallpaper the most according to claim 5, it is characterised in that: further comprise the steps of: described PVC wallpaper At 100～120 DEG C, 60～90s it are dried before spraying.
9. an appendix has the mildew-proof wallpaper of medicine carrying chitosan, it is characterised in that: it includes PVC wallpaper layer, described PVC wallpaper layer For the PVC wallpaper with Plant fiber's body paper as base material, described mildew-proof wallpaper also includes the Plant fiber's body paper being coated in PVC wallpaper Medicine carrying chitosan layer on substrate surface, the medicine carrying chitosan in described medicine carrying chitosan layer is by the described side of one of Claims 1 to 4 Prepared by method.
Mildew-proof wallpaper the most according to claim 9, it is characterised in that: described medicine carrying chitosan layer is micro-by medicine carrying chitosan Ball Emulsion Spraying is formed on Plant fiber's raw base paper face of PVC wallpaper, and described medicine carrying chitosan microball emulsion is in PVC wallpaper On quantity for spray be 0.5～4mL/m2。
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CN117659936A (en) * 2024-01-31 2024-03-08 山东沃赛新材料科技有限公司 Preparation method of environment-friendly super-strong mildew-proof matte de-esterification type beautifying and edge-finishing sealant

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