WO2021232534A1 - 一种抗病毒抗菌功能薄膜及其制备方法 - Google Patents

一种抗病毒抗菌功能薄膜及其制备方法 Download PDF

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WO2021232534A1
WO2021232534A1 PCT/CN2020/098076 CN2020098076W WO2021232534A1 WO 2021232534 A1 WO2021232534 A1 WO 2021232534A1 CN 2020098076 W CN2020098076 W CN 2020098076W WO 2021232534 A1 WO2021232534 A1 WO 2021232534A1
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antibacterial
antiviral
agent
inorganic
nano
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PCT/CN2020/098076
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English (en)
French (fr)
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陈晓东
李毕忠
杨明
施克炜
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太湖金张科技股份有限公司
北京崇高纳米科技有限公司
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Publication of WO2021232534A1 publication Critical patent/WO2021232534A1/zh

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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/10—Esters of organic acids
    • C09D101/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09D109/02—Copolymers with acrylonitrile
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    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
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    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
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    • C09J2467/006—Presence of polyester in the substrate
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    • C09J2483/00—Presence of polysiloxane

Definitions

  • This application relates to the technical field of functional films, in particular to an antiviral and antibacterial functional film and a preparation method thereof.
  • CN105348756B discloses an antibacterial polyester film and its preparation method and its use. Nano silver is dispersed in polyester chips to prepare antibacterial film products, and its antibacterial rate against Escherichia coli and Staphylococcus aureus is ⁇ 99%. Although the above-mentioned film has good antibacterial properties, it also has the problems of low dispersion of nano-silver materials in polyester chips, uneven antibacterial properties, complicated preparation processes and inconvenient application.
  • this application proposes an anti-viral and anti-bacterial functional film and a preparation method thereof.
  • the functional film has excellent anti-virus and anti-bacterial effects, and has uniform and long-lasting anti-virus and anti-bacterial properties.
  • An antiviral and antibacterial functional film proposed in the present application includes a substrate, an antiviral and antibacterial coating fixed on the upper surface of the substrate, and a low-viscosity organic glue layer fixed on the lower surface of the substrate layer; the antiviral and antibacterial coating The layer is obtained by coating a coating solution containing a nano-inorganic/organic composite antiviral and antibacterial treatment agent and a transparent resin on the substrate.
  • the nano inorganic/organic composite antiviral and antibacterial treatment agent is nano silver ion inorganic/organic composite antiviral and antibacterial treatment agent, nano copper ion inorganic/organic composite antiviral and antibacterial treatment agent, nano zinc ion inorganic/organic composite antiviral treatment agent
  • One or more of the antibacterial treatment agents; among them, the nano-inorganic/organic composite antiviral and antibacterial treatment agent accounts for 0.1-20% of the total weight of the coating liquid.
  • the coating liquid is composed of the following components by weight: 0.1-20 parts of nano inorganic/organic composite anti-viral and anti-bacterial treatment agent, 2-20 parts of transparent resin, 10-35 parts of cosolvent, and 0.02-2 parts of dispersant. Parts, 20 to 65 parts of water.
  • the preparation of the nano-inorganic/organic composite antiviral and antibacterial treatment agent is as follows: dissolve the organic antibacterial agent in a solvent, add water, then add a polymer binder, heat up and stir to obtain a milky solution, cool, and add inorganic
  • the antibacterial agent is obtained by stirring; wherein, the inorganic antibacterial agent is nano antibacterial sol, which is one or more of nano silver sol, nano copper sol, and nano zinc sol; wherein, the organic antibacterial agent is an organic sulfur compound, which is a double One or more of trichloromethyl sulfone, allicin, dibenzoyl disulfide, halopicolinium sulfide, mercaptopyridine, pentachlorothiophenol, and 2-thiocyanomethylthiobenzothiazole.
  • the transparent resin is polyvinyl alcohol, polymethyl methacrylate, polyacrylate, cellulose triacetate, polyamide, polyurethane resin, polyethylene, polypropylene, ethylene-propylene copolymer, styrene acrylonitrile, One of polystyrene, nitrocellulose, polyvinyl butyral, methyl methacrylate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, neoprene, nitrile rubber, butadiene rubber, or Many kinds.
  • the co-solvent is ethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerol, diglycerol, triglycerol, isopropanol, methyl acetate, ethyl acetate, propylene glycol, One or more of ethylene glycol monobutyl ether, polyethylene glycol with a degree of polymerization of 55 or less, and pentaerythritol.
  • the dispersant is one or more of cationic or nonionic dispersants;
  • the cationic dispersant is stearylamine acetate, alkyl quaternary ammonium salt, aminopropylamine dioleate, quaternary amine Salt, one or more of specially modified polyamino amide phosphate;
  • non-ionic dispersant is the adduct of fatty acid ethylene oxide C 17 H 33 COO(CH 2 CH 2 O) n H, poly One or more of ethylene glycol polyol and polyethyleneimine derivatives.
  • the coating liquid further includes 0.001 to 1.0 parts of anti-fingerprint agent and 0.005 to 5.0 parts of anti-fogging agent.
  • the thickness of the antiviral and antibacterial coating is 0.2-20 ⁇ m.
  • the material of the substrate is any one of BOPP, BOPET, BOPA, PET, PE, PC, TAC, PP, PS, PMMA, TPU, PI, PVB, and PVC.
  • the low-viscosity organic adhesive layer is an acrylic adhesive layer, a silicone pressure-sensitive adhesive, a rubber-type pressure-sensitive adhesive, and a polyurethane pressure-sensitive adhesive layer.
  • This application proposes a method for preparing an antiviral and antibacterial functional film, which includes the following steps:
  • the above preparation method includes the following steps:
  • the coating process can be, but not limited to, gravure coating, micro-gravure coating, screen coating and spraying processes; high pressure can be used
  • the mercury lamp cures the above coating.
  • the coating can be cured by but not limited to thermal curing process, solvent-based UV curing process, solvent-based electron beam curing process, solvent-free UV curing process, and solvent-free electron beam curing process.
  • S2 also includes adding an anti-fingerprint agent and an anti-fogging agent to the white emulsion to prepare a coating liquid.
  • the anti-viral and anti-bacterial functional film proposed in this application is coated with an anti-viral and anti-bacterial coating on the substrate.
  • the nano-inorganic/organic composite anti-viral and anti-bacterial The treatment agent and the transparent resin are effectively mixed to prepare a composite material that can be used in the coating solution.
  • the obtained antiviral and antibacterial coating forms a phase separation.
  • the nano-inorganic/organic composite antiviral and antibacterial treatment agent gathers on the surface with a high concentration, so that the film can be more Strong anti-virus and antibacterial effect, and the anti-virus and antibacterial performance is uniform and long-lasting.
  • the coating also has good anti-scratch, anti-fingerprint, anti-fog, abrasion resistance, weather resistance and other properties.
  • the low-viscosity organic glue layer fixed under the substrate can automatically vent, and it is easy to stick to the surface of metal, wood, plastic, and glass. It is convenient to use, and is non-irritating and non-toxic to human skin.
  • the preparation method of the present application is simple and low in cost, and is expected to be used in the industrial production of antibacterial film products.
  • An antiviral and antibacterial functional film proposed in the present application includes a substrate, an antiviral and antibacterial coating fixed on the upper surface of the substrate, and a low-viscosity organic glue layer fixed on the lower surface of the substrate layer;
  • the material of the substrate is PET;
  • the low-viscosity organic adhesive layer is an acrylic adhesive layer;
  • the thickness of the anti-viral and anti-bacterial coating is 0.2 ⁇ m, which is obtained by coating a coating solution containing a nano-inorganic/organic composite anti-viral and anti-bacterial treatment agent and a transparent resin on the substrate;
  • the coating liquid is composed of the following components by weight: 20 parts of nano inorganic/organic composite antiviral and antibacterial treatment agent, 10 parts of transparent resin, 25 parts of cosolvent, 1 part of dispersant, 0.5 part of anti-fingerprint agent, anti-fingerprint 3.5 parts of aerosol and 40 parts of water.
  • the preparation of the nano-inorganic/organic composite anti-viral and anti-bacterial treatment agent is as follows: dissolve the organic anti-bacterial agent in a solvent, add water, then add a polymer binder, heat up and stir to obtain a milky solution, cool, and add an inorganic anti-bacterial agent to it , Stir, and get;
  • the inorganic antibacterial agent is nano silver sol;
  • the organic antibacterial agent is a mixture of bis(trichloromethyl sulfone) and 2-thiocyanomethylthiobenzothiazole.
  • the transparent resin is butadiene rubber; the co-solvent is a mixture of ethanol and methyl acetate; the dispersant is stearylamine acetate.
  • the preparation method of the anti-virus and anti-bacterial functional film includes the following steps:
  • An antiviral and antibacterial functional film proposed in the present application includes a substrate, an antiviral and antibacterial coating fixed on the upper surface of the substrate, and a low-viscosity organic glue layer fixed on the lower surface of the substrate layer;
  • the material of the substrate is BOPP;
  • the low-viscosity organic adhesive layer is silicone pressure-sensitive adhesive;
  • the thickness of the anti-viral and anti-bacterial coating is 20 ⁇ m, which is obtained by coating the substrate with a coating solution containing a nano-inorganic/organic composite anti-viral and anti-bacterial treatment agent and a transparent resin;
  • the coating liquid is composed of the following components by weight: 1.5 parts of nano-inorganic/organic composite antiviral and antibacterial treatment agent, 20 parts of transparent resin, 35 parts of cosolvent, 2 parts of dispersant, 1.0 part of anti-fingerprint agent, anti-fingerprint agent 5.0 parts of mist and 65 parts of water.
  • the preparation of the nano-inorganic/organic composite anti-viral and anti-bacterial treatment agent is as follows: dissolve the organic anti-bacterial agent in a solvent, add water, then add a polymer binder, heat up and stir to obtain a milky solution, cool, and add an inorganic anti-bacterial agent to it , Stir, and get;
  • the inorganic antibacterial agent is nano copper sol;
  • the organic antibacterial agent is mercaptopyridine.
  • the transparent resin is a mixture of polyvinyl alcohol and polymethyl methacrylate; the co-solvent is a mixture of ethanol and ethylene glycol monobutyl ether; and the dispersant is a polyethylene glycol polyol.
  • the preparation method of the aforementioned antiviral and antibacterial functional film is the same as that of Example 1, except that the pH of the emulsion is adjusted to 8.0 in S1.
  • An antiviral and antibacterial functional film proposed in the present application includes a substrate, an antiviral and antibacterial coating fixed on the upper surface of the substrate, and a low-viscosity organic glue layer fixed on the lower surface of the substrate layer;
  • the material of the substrate is PMMA;
  • the low-viscosity organic adhesive layer is silicone pressure-sensitive adhesive;
  • the thickness of the anti-viral and anti-bacterial coating is 5 ⁇ m, which is obtained by coating a coating solution containing a nano inorganic/organic composite anti-viral and anti-bacterial treatment agent and a transparent resin on the substrate;
  • the coating liquid is composed of the following components by weight: 0.33 parts of nano inorganic/organic composite antiviral and antibacterial treatment agent, 2 parts of transparent resin, 10 parts of cosolvent, 0.02 part of dispersant, 0.001 part of anti-fingerprint agent, anti-fingerprint agent 0.005 parts of aerosol and 20 parts of water.
  • the preparation of the nano-inorganic/organic composite anti-viral and anti-bacterial treatment agent is as follows: dissolve the organic anti-bacterial agent in a solvent, add water, then add a polymer binder, heat up and stir to obtain a milky solution, cool, and add an inorganic anti-bacterial agent to it , Stir and obtain; wherein, the inorganic antibacterial agent is composed of nano silver sol and nano zinc sol in a weight ratio of 3:1; and the organic antibacterial agent is 2-thiocyanomethylthiobenzothiazole.
  • the transparent resin is a mixture of cellulose triacetate and vinyl chloride-vinyl acetate copolymer; the co-solvent is a mixture of ethanol, ethyl acetate, and polyethylene glycol with a degree of polymerization of 55 or less; and the dispersant is a quaternary ammonium salt.
  • the preparation method of the antiviral and antibacterial functional film is the same as that of Example 1, except that the pH of the emulsion is adjusted to 5.0 in S1.
  • An antiviral and antibacterial functional film proposed in the present application includes a substrate, an antiviral and antibacterial coating fixed on the upper surface of the substrate, and a low-viscosity organic glue layer fixed on the lower surface of the substrate layer;
  • the material of the substrate is PVC;
  • the low-viscosity organic adhesive layer is polyurethane pressure-sensitive adhesive;
  • the thickness of the anti-viral and anti-bacterial coating is 10 ⁇ m, which is obtained by coating a coating solution containing a nano-inorganic/organic composite anti-viral and anti-bacterial treatment agent and a transparent resin on the substrate;
  • the coating liquid is composed of the following components by weight: 8.5 parts of nano inorganic/organic composite antiviral and antibacterial treatment agent, 15 parts of transparent resin, 30 parts of cosolvent, 0.05 part of dispersant, 0.01 part of anti-fingerprint agent, anti-fingerprint agent 1 part of aerosol and 40 parts of water.
  • the preparation of the nano-inorganic/organic composite anti-viral and anti-bacterial treatment agent is as follows: dissolve the organic anti-bacterial agent in a solvent, add water, then add a polymer binder, heat up and stir to obtain a milky solution, cool, and add an inorganic anti-bacterial agent to it , Stir, and get; the inorganic antibacterial agent is nano silver sol; the organic antibacterial agent is a mixture of bistrichloromethyl sulfone and allicin.
  • the transparent resin is nitrile rubber; the co-solvent is a mixture of isopropanol and ethylene glycol monobutyl ether; the dispersant is the adduct of octadecenamine acetate and fatty acid ethylene oxide C 17 H 33 COO( CH 2 CH 2 O) a mixture of n H.
  • the preparation method of the antiviral and antibacterial functional film is the same as that of Example 1, except that the pH of the emulsion is adjusted to 6.0 in S1.
  • Example 2 A kind of film, compared with Example 1, the only difference is that it does not contain an antiviral and antibacterial coating.
  • Virus for detection Influenza A virus H1N1 (A/PR/8/34) MDCK cells;
  • Escherichia coli ATCC 25922
  • Staphylococcus aureus ATCC 6538
  • Candida albicans AS 2.208

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Abstract

一种抗病毒抗菌功能薄膜及其制备方法，该功能薄膜包括基材、抗病毒抗菌涂层，以及低粘有机胶层；抗病毒抗菌涂层是由含纳米无机/有机复合抗病毒抗菌处理剂和透明树脂的涂布液在基材上涂布得到的。通过采用合理的工艺和对透明树脂等配方原料的合理选择，从而有效将含抗病毒抗菌处理剂涂布在基材表面，抗病毒抗菌效果明显，且抗病毒抗菌性能均匀、长效。

Description

一种抗病毒抗菌功能薄膜及其制备方法
本申请要求于2020年05月19日提交中国专利局、申请号为202010425174.8、申请名称为一种抗病毒抗菌功能薄膜及其制备方法的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及功能薄膜技术领域，尤其涉及一种抗病毒抗菌功能薄膜及其制备方法。
背景技术
近年来，新型流感、新型冠状、埃博拉等各种病毒、肺炎克雷伯菌等细菌所致的感染症已威胁到人类的生命，特别是近十几年爆发的几次由病毒传播感染引起的大规模疫情，造成全世界大量的人员伤亡和经济损失，因此在世界范围内急需寻找应对策略。
使用次氯酸、过氧化氢等化学杀菌试剂能够消灭细菌、病毒等微生物的病原体，但抗菌效果持续性低、无法达到长效抗菌，从而不能有效防止接触传染。因此，对具有长效抗菌抗病毒功效的功能膜材料的需求提高。CN105348756B公开了一种抗菌聚酯薄膜及其制备方法与它的用途，将纳米银分散在聚酯切片中制备抗菌性薄膜制品，其对大肠杆菌和金黄色葡萄球菌的抗菌率≥99％。虽然上述薄膜具有良好的抗菌性，但也存在着纳米银材料在聚酯切片中分散性低，抗菌性不均的问题，且制备工艺复杂、应用不方便。
申请内容
基于背景技术存在的技术问题，本申请提出了一种抗病毒抗菌功能薄膜及 其制备方法，该功能薄膜抗病毒抗菌效果优异，且抗病毒抗菌性能均匀、长效。
本申请提出的一种抗病毒抗菌功能薄膜，包括基材、固着在基材上表面的抗病毒抗菌涂层，以及固着在基材层下表面的低粘有机胶层；所述抗病毒抗菌涂层是由含纳米无机/有机复合抗病毒抗菌处理剂和透明树脂的涂布液在基材上涂布得到的。
其中，所述纳米无机/有机复合抗病毒抗菌处理剂为纳米银离子无机/有机复合抗病毒抗菌处理剂、纳米铜离子无机/有机复合抗病毒抗菌处理剂、纳米锌离子无机/有机复合抗病毒抗菌处理剂中的一种或多种；其中，纳米无机/有机复合抗病毒抗菌处理剂占涂布液总重量的0.1～20％。
其中，所述涂布液由以下重量份的组分组成：纳米无机/有机复合抗病毒抗菌处理剂0.1～20份、透明树脂2～20份、助溶剂10～35份、分散剂0.02～2份、水20～65份。
其中，所述纳米无机/有机复合抗病毒抗菌处理剂的制备如下：将有机抗菌剂溶于溶剂中，加水，再加入高分子粘合剂，升温搅拌，得乳状溶液，冷却，向其中加入无机抗菌剂，搅拌，即得；其中，无机抗菌剂为纳米抗菌溶胶，为纳米银溶胶、纳米铜溶胶、纳米锌溶胶中的一种或多种；其中，有机抗菌剂为有机硫化合物，为双三氯甲砜、大蒜素、双苯甲酰二硫、卤代吡啶甲硫醚、巯基吡啶、五氯硫酚和2-硫氰基甲基硫代苯并噻唑中的一种或多种。
其中，所述透明树脂为聚乙烯醇、聚甲基丙烯酸甲酯、聚丙烯酸酯、三醋酸纤维素、聚酰胺、聚氨酯树脂、聚乙烯、聚丙烯、乙烯-丙烯共聚物、苯乙烯丙烯腈、聚苯乙烯、硝酸纤维素、聚乙烯醇缩丁醛、甲丙烯甲酯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、氯丁橡胶、丁腈橡胶、顺丁橡胶中的一种或多种。
其中，助溶剂为乙醇、乙二醇、二乙二醇、三乙二醇、丙二醇、丙三醇、二甘油、三甘油、异丙醇、乙酸甲酯、乙酸乙酯、丙烯乙二醇、乙二醇单丁基醚、聚合度55以下的聚乙二醇、季戊四醇中的一种或多种。
其中，分散剂为阳离子型或非离子型分散剂中的一种或多种；阳离子型分散剂为十八碳烯胺醋酸盐、烷基季铵盐、氨基丙胺二油酸酯、季胺盐、特殊改性的多氨基酰胺磷酸盐中的一种或多种；非离子型分散剂为脂肪酸环氧乙烷的加成物C 17H 33COO(CH 2CH 2O) nH、聚乙二醇型多元醇、聚乙烯亚胺衍生物中的一种或多种。
其中，所述涂布液还包括防指纹剂0.001～1.0份、防雾剂0.005～5.0份。
其中，所述抗病毒抗菌涂层的厚度为0.2～20μm。
其中，所述基材的材质为BOPP、BOPET、BOPA、PET、PE、PC、TAC、PP、PS、PMMA、TPU、PI、PVB、PVC中的任意一种。
其中，所述低粘有机胶层为丙烯酸胶层、有机硅压敏胶、橡胶型压敏胶、聚氨酯压敏胶层。
本申请提出了一种抗病毒抗菌功能薄膜的制备方法，包括以下步骤：
S1、将纳米无机/有机复合抗病毒抗菌处理剂和分散剂加入到配料罐中，搅拌；然后将助溶剂加到配料罐中，搅拌，得到乳液；向乳液中加入水，继续搅拌，然后调节乳液pH至2.0-8.0，搅拌；
S2、在搅拌下，将透明树脂加入到在S1的乳液中，搅拌，冷却，即得涂布液；
S3、将涂布液均匀涂布在透明的基材薄膜表面，固化。
具体的，上述制备方法，包括以下步骤：
S1、将纳米无机/有机复合抗病毒抗菌处理剂和分散剂加入到配料罐中，在 60-70℃下进行搅拌，搅拌速度为100-5000r/min，搅拌时间为5-300min；然后将助溶剂加到配料罐中，在60-70℃下进行搅拌，搅拌速度为100-5000r/min，搅拌时间5-300min，得到均匀的乳液；向乳液中加入水，继续搅拌，搅拌速度为100-5000r/min，搅拌时间为5-300min；然后调节乳液pH至2.0-8.0，搅拌均匀；
S2、在搅拌下，将透明树脂加入到在S1的乳液中，在40-50℃的下进行搅拌，搅拌速度为100-5000r/min，搅拌时间为5-300min，然后冷却至室温，即得涂布液；
S3、将涂布液均匀涂布在透明的基材薄膜表面，固化；其中，涂布工艺可以采用但不限于凹版涂布、微凹版涂布、丝网涂布和喷涂等工艺；可以使用高压汞灯将上述涂层固化，涂层固化可以通过但不限于热固化工艺、有溶剂型UV固化工艺、有溶剂型电子束固化工艺、无溶剂型UV固化工艺和无溶剂型电子束固化工艺。
其中，S2中，还包括向白色乳状液中加入防指纹剂和防雾剂制备涂布液。
本申请提出的抗病毒抗菌功能薄膜，在基材上涂布一层抗病毒抗菌涂层，通过采用合理的工艺和对透明树脂等配方原料的合理选择，从而将纳米无机/有机复合抗病毒抗菌处理剂和透明树脂有效混合，制备可用于涂布液的复合材料，得到的抗病毒抗菌涂层形成相分离，纳米无机/有机复合抗病毒抗菌处理剂集聚在表面浓度高，从而使得薄膜获得更强的抗病毒抗菌效果，且抗病毒抗菌性能均匀、长效。此外，该涂层还具有良好的防刮、防指纹、防雾，耐磨、耐候性能等性能。基材下固着的低粘有机胶层能够自动排气，容易贴附于金属、木材、塑料、玻璃表面，使用方便，且对人体皮肤无刺激、无毒。本申请的制备方法简单，成本较低，有望用于抗菌性薄膜制品的工业化生产。
具体实施方式
下面，通过具体实施例对本申请的技术方案进行详细说明。
实施例1
本申请提出的一种抗病毒抗菌功能薄膜，包括基材、固着在基材上表面的抗病毒抗菌涂层，以及固着在基材层下表面的低粘有机胶层；
其中，基材的材质为PET；低粘有机胶层为丙烯酸胶层；
抗病毒抗菌涂层的厚度为0.2μm，其是由含纳米无机/有机复合抗病毒抗菌处理剂和透明树脂的涂布液在基材上涂布得到的；
具体的，涂布液由以下重量份的组分组成：纳米无机/有机复合抗病毒抗菌处理剂20份、透明树脂10份、助溶剂25份、分散剂1份、防指纹剂0.5份、防雾剂3.5份、水40份。
其中，纳米无机/有机复合抗病毒抗菌处理剂的制备如下：将有机抗菌剂溶于溶剂中，加水，再加入高分子粘合剂，升温搅拌，得乳状溶液，冷却，向其中加入无机抗菌剂，搅拌，即得；其中，无机抗菌剂为纳米银溶胶；有机抗菌剂为双三氯甲砜和2-硫氰基甲基硫代苯并噻唑的混合物。
透明树脂为顺丁橡胶；助溶剂为乙醇和乙酸甲酯的混合物；分散剂十八碳烯胺醋酸盐。
上述抗病毒抗菌功能薄膜的制备方法，包括以下步骤：
S1、将纳米无机/有机复合抗病毒抗菌处理剂和分散剂加入到配料罐中，在65℃下进行搅拌，搅拌速度为2000r/min，搅拌时间为120min；然后将助溶剂加到配料罐中，在70℃下进行搅拌，搅拌速度为3500r/min，搅拌时间180min，得到一种均匀的乳液；向乳液中加入水，继续搅拌，搅拌速度为4000r/min，搅拌时间为30min；然后调节乳液pH至2.0，搅拌均匀；
S2、在搅拌下，将透明树脂加入到在S1中得到的乳液中，在45℃的下进行 搅拌，搅拌速度为2500r/min，搅拌时间为150min，然后冷却至室温，再向其中加入防指纹剂和防雾剂制备涂布液，搅拌，即得涂布液；
S3、将涂布液均匀涂布在透明的基材薄膜表面，固化。
实施例2
本申请提出的一种抗病毒抗菌功能薄膜，包括基材、固着在基材上表面的抗病毒抗菌涂层，以及固着在基材层下表面的低粘有机胶层；
其中，基材的材质为BOPP；低粘有机胶层为有机硅压敏胶；
抗病毒抗菌涂层的厚度为20μm，其是由含纳米无机/有机复合抗病毒抗菌处理剂和透明树脂的涂布液在基材上涂布得到的；
具体的，涂布液由以下重量份的组分组成：纳米无机/有机复合抗病毒抗菌处理剂1.5份、透明树脂20份、助溶剂35份、分散剂2份、防指纹剂1.0份、防雾剂5.0份、水65份。
其中，纳米无机/有机复合抗病毒抗菌处理剂的制备如下：将有机抗菌剂溶于溶剂中，加水，再加入高分子粘合剂，升温搅拌，得乳状溶液，冷却，向其中加入无机抗菌剂，搅拌，即得；其中，无机抗菌剂为纳米铜溶胶；有机抗菌剂为巯基吡啶。
透明树脂为聚乙烯醇、聚甲基丙烯酸甲酯的混合物；助溶剂为乙醇和乙二醇单丁基醚混合物；分散剂为聚乙二醇型多元醇。
上述抗病毒抗菌功能薄膜的制备方法同实施例1，区别仅在于S1中调节乳液的pH至8.0。
实施例3
本申请提出的一种抗病毒抗菌功能薄膜，包括基材、固着在基材上表面的抗病毒抗菌涂层，以及固着在基材层下表面的低粘有机胶层；
其中，基材的材质为PMMA；低粘有机胶层为有机硅压敏胶；
抗病毒抗菌涂层的厚度为5μm，其是由含纳米无机/有机复合抗病毒抗菌处理剂和透明树脂的涂布液在基材上涂布得到的；
具体的，涂布液由以下重量份的组分组成：纳米无机/有机复合抗病毒抗菌处理剂0.33份、透明树脂2份、助溶剂10份、分散剂0.02份、防指纹剂0.001份、防雾剂0.005份、水20份。
其中，纳米无机/有机复合抗病毒抗菌处理剂的制备如下：将有机抗菌剂溶于溶剂中，加水，再加入高分子粘合剂，升温搅拌，得乳状溶液，冷却，向其中加入无机抗菌剂，搅拌，即得；其中，无机抗菌剂为纳米银溶胶和纳米锌溶胶按照3：1的重量比组成的；有机抗菌剂为2-硫氰基甲基硫代苯并噻唑。
透明树脂为三醋酸纤维素、氯乙烯-乙酸乙烯酯共聚物的混合物；助溶剂为乙醇、乙酸乙酯、聚合度55以下的聚乙二醇的混合物；分散剂为季胺盐。
上述抗病毒抗菌功能薄膜的制备方法同实施例1，区别仅在于S1中调节乳液的pH至5.0。
实施例4
本申请提出的一种抗病毒抗菌功能薄膜，包括基材、固着在基材上表面的抗病毒抗菌涂层，以及固着在基材层下表面的低粘有机胶层；
其中，基材的材质为PVC；低粘有机胶层为聚氨酯压敏胶；
抗病毒抗菌涂层的厚度为10μm，其是由含纳米无机/有机复合抗病毒抗菌处 理剂和透明树脂的涂布液在基材上涂布得到的；
具体的，涂布液由以下重量份的组分组成：纳米无机/有机复合抗病毒抗菌处理剂8.5份、透明树脂15份、助溶剂30份、分散剂0.05份、防指纹剂0.01份、防雾剂1份、水40份。
其中，纳米无机/有机复合抗病毒抗菌处理剂的制备如下：将有机抗菌剂溶于溶剂中，加水，再加入高分子粘合剂，升温搅拌，得乳状溶液，冷却，向其中加入无机抗菌剂，搅拌，即得；无机抗菌剂为纳米银溶胶；有机抗菌剂为双三氯甲砜和大蒜素的混合物。
透明树脂为丁腈橡胶；助溶剂为异丙醇和乙二醇单丁基醚的混合物；分散剂为十八碳烯胺醋酸盐和脂肪酸环氧乙烷的加成物C 17H 33COO(CH 2CH 2O) nH的混合物。
上述抗病毒抗菌功能薄膜的制备方法同实施例1，区别仅在于S1中调节乳液的pH至6.0。
对比例
一种薄膜，与实施例1相比，区别仅在于不含有抗病毒抗菌涂层。
对本申请实施例1-4制备的抗病毒抗菌功能薄膜和对比例制备的薄膜进行性能测试，结果见表1。
抗病毒活性抗菌性测定：
A、参照标准及方法：ISO 21702-2019“塑料和其他多孔表面抗病毒活性测定”、GB/T 31402-2015“塑料塑料表面抗菌性能测试方法”；
B、检测用病毒：甲型流感病毒H1N1(A/PR/8/34)MDCK细胞；
检测用细菌：大肠杆菌(ATCC 25922)、金黄色葡萄球菌(ATCC 6538)、白色念珠菌(AS 2.208)；
表1实施例1-4和对比例制备的薄膜的抗病毒抗菌性能测试结果
Figure PCTCN2020098076-appb-000001
从表1中可以看出，本申请实施例1-4中制备的功能薄膜的抗病毒活性率及抗菌率均达到99.90％以上，抗病毒抗菌性能优异。
以上所述，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，根据本申请的技术方案及其申请构思加以等同替换或改变，都应涵盖在本申请的保护范围之内。

Claims (10)

  1. 一种抗病毒抗菌功能薄膜，其中，包括基材、固着在基材上表面的抗病毒抗菌涂层，以及固着在基材层下表面的低粘有机胶层；所述抗病毒抗菌涂层是由含纳米无机/有机复合抗病毒抗菌处理剂和透明树脂的涂布液在基材上涂布得到的。
  2. 根据权利要求1所述的抗病毒抗菌功能薄膜，其中，所述纳米无机/有机复合抗病毒抗菌处理剂为纳米银离子无机/有机复合抗病毒抗菌处理剂、纳米铜离子无机/有机复合抗病毒抗菌处理剂、纳米锌离子无机/有机复合抗病毒抗菌处理剂中的一种或多种；其中，纳米无机/有机复合抗病毒抗菌处理剂占涂布液总重量的0.1～20％。
  3. 根据权利要求2所述的抗病毒抗菌功能薄膜，其中，所述涂布液由以下重量份的组分组成：纳米无机/有机复合抗病毒抗菌处理剂0.1～20份、透明树脂2～20份、助溶剂10～35份、分散剂0.02～2份、水20～65份。
  4. 根据权利要求2所述的抗病毒抗菌功能薄膜，其中，所述纳米无机/有机复合抗病毒抗菌处理剂的制备如下：将有机抗菌剂溶于溶剂中，加水，再加入高分子粘合剂，升温搅拌，得乳状溶液，冷却，向其中加入无机抗菌剂，搅拌，即得；其中，无机抗菌剂为纳米抗菌溶胶；其中，有机抗菌剂为有机硫化合物。
  5. 根据权利要求3所述的抗病毒抗菌功能薄膜，其中，所述透明树脂为聚乙烯醇、聚甲基丙烯酸甲酯、聚丙烯酸酯、三醋酸纤维素、聚酰胺、聚氨酯树脂、聚乙烯、聚丙烯、乙烯-丙烯共聚物、苯乙烯丙烯腈、聚苯乙烯、硝酸纤维素、聚乙烯醇缩丁醛、甲丙烯甲酯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、氯丁橡胶、丁腈橡胶、顺丁橡胶中的一种或多种。
  6. 根据权利要求3所述的抗病毒抗菌功能薄膜，其中，所述涂布液还包括防指纹剂0.001～1.0份、防雾剂0.005～5.0份。
  7. 根据权利要求1所述的抗病毒抗菌功能薄膜，其中，所述抗病毒抗菌涂层的厚度为0.2～20μm。
  8. 根据权利要求1所述的抗病毒抗菌功能薄膜，其中，所述基材的材质为BOPP、BOPET、BOPA、PET、PE、PC、TAC、PP、PS、PMMA、TPU、PI、PVB、PVC中的任意一种。
  9. 一种抗病毒抗菌功能薄膜的制备方法，其中，包括以下步骤：
    S1、将纳米无机/有机复合抗病毒抗菌处理剂和分散剂加入到配料罐中，搅拌；然后将助溶剂加到配料罐中，搅拌，得到乳液；向乳液中加入水，继续搅拌，然后调节乳液pH至2.0-8.0，搅拌；
    S2、在搅拌下，将透明树脂加入到在S1的乳液中，搅拌，冷却，即得涂布液；
    S3、将涂布液均匀涂布在透明的基材薄膜表面，固化。
  10. 根据权利要求9所述的抗病毒抗菌功能薄膜的制备方法，其中，S2中，还包括向已加入透明树脂的乳液中加入防指纹剂和防雾剂制备涂布液。
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