CN111040221A - 一种抗菌自清洁膜及其制备方法和应用 - Google Patents

一种抗菌自清洁膜及其制备方法和应用 Download PDF

Info

Publication number
CN111040221A
CN111040221A CN201910126016.XA CN201910126016A CN111040221A CN 111040221 A CN111040221 A CN 111040221A CN 201910126016 A CN201910126016 A CN 201910126016A CN 111040221 A CN111040221 A CN 111040221A
Authority
CN
China
Prior art keywords
titanium dioxide
film
antibacterial
layer
self
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910126016.XA
Other languages
English (en)
Other versions
CN111040221B (zh
Inventor
王荣
徐婷
付俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN201910126016.XA priority Critical patent/CN111040221B/zh
Publication of CN111040221A publication Critical patent/CN111040221A/zh
Application granted granted Critical
Publication of CN111040221B publication Critical patent/CN111040221B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plant Pathology (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明公开了一种含多层涂层结构的自清洁抗菌膜，其包括基材、二氧化钛交联层和氟化层。本发明公开的制备方法包括：对光学薄膜表面进行活化处理，在薄膜表面引入二氧化钛纳米颗粒，并对表面进行微纳米结构处理，最后对表面进行氟化处理，获得兼具光催化杀菌与超疏水防污性能的功能性涂层，可抑制细菌黏附生长，降低污染物吸附，同时具有良好的透光性能，可应用于各类电子设备触摸屏。

Description

一种抗菌自清洁膜及其制备方法和应用
技术领域
本发明涉及功能性薄膜技术领域，具体来讲，涉及一种抗菌自清洁膜、其制备方法和应用。
背景技术
随着国民经济的快速发展，触屏式电子设备被广泛地用于人们日常生活和医疗卫生系统中。但是，触摸屏表面易沾染细菌，成为细菌繁殖滋生的场所，各类致病菌极易通过触摸屏传播疾病。近年来，多项国内外研究表明，包括医院电子设备屏幕、智能手机屏幕、餐厅自助点餐屏等表面含有大量细菌，其中包括多种耐药细菌。公共场所特别是医院、高铁站、餐厅等处电子触摸屏的细菌污染对公众健康安全构成了极大的威胁，受到人们越来越多的重视。日常的清洁处理措施往往难以实施到位，无法有效地杀死细菌。
因此，需要一种应用于触摸屏的抗菌薄膜，保护其表面免受细菌黏附与增殖，降低感染性病菌通过电子屏幕传播的可能性。
现有的抗菌透明薄膜通常负载银、铜等金属离子，通过杀菌剂的释放杀死细菌。例如，中国专利CN105348756A公开了一种抗菌聚酯薄膜及其制备方法。其通过纳米银单质粉体与变色抑制剂、偶联分散剂、乙醇等混合，并将其与聚酯切片混合后通过熔融挤出后获得纳米银抗菌母粒，再将其与聚酯切片混合熔融挤出并拉伸得到抗菌薄膜。中国专利CN105176342A公开了一种纳米抗菌防指纹药液材料的制备方法及应用。其将甲基九氟丁醚、乙基全氟丁基醚、乙基九氟代丁基醚、全氟硅油、全氟聚醚烷氧基硅烷等含氟有机物与纳米银离子颗粒混合获得纳米抗菌防指纹药液，涂覆于手机盖板上形成薄膜。中国专利CN106397961A公开了一种抗菌超透明EVA膜及制备方法。其将EVA粒子、银系无机抗菌剂、纳米二氧化硅等混合后制备母粒，通过挤出延流、冷却定型获得抗菌超透明EVA膜。中国专利CN106317726A公开了一种用于触摸屏表面的抗菌水凝胶的制备方法。其是将纳米氧化亚铜负载至卡波姆中获得抗菌水凝胶，将其涂敷在触摸屏表面干燥后形成抗菌薄膜。上述方法所用的金属纳米颗粒或者金属离子具有一定的毒性，对人体健康以及环境安全构成潜在威胁。并且，其杀菌性能随着金属离子的释放损耗而逐渐降低。
二氧化钛是一种光触媒，其在一定波长范围内的光量子照射下，其价带电子被激发，跃迁到导带形成自由电子，而在价带形成一个带正电的空穴，形成电子-空穴对。空穴的氧化能力与自由电子的还原能力可使与其接触的H2O、O2等反应形成活性自由基。这些自由基团与细菌作用，破坏其结构，具有强烈的杀菌能力。其光催化杀菌的特性使其在光照条件下可持续产生杀菌活性物质，本身不发生损耗，从而具有长效抗菌能力。并且光催化产生的自由基在环境中半衰期较短，对人体与环境安全无害。因此，二氧化钛是一种极具潜力的新型杀菌剂。中国专利CN102898875A公开了一种纳米自清洁抗菌涂层液。其将含有粒径小于50nm的二氧化钛颗粒以及V、Cr等元素的乙醇溶液，涂覆于基材表面，通过高温处理形成薄膜，在有无光线情况下均可工作，具有抗菌、除臭、抗氧化等功能。然而，上述涂层通过物理吸附基材表面，稳定性和长效性难以得到保证。中国专利CN108299663A公开了一种防指纹抗菌膜。其包括基材层与硬化层，硬化层中含有氮掺杂的二氧化钛光催化剂，硬化层通过紫外光固化树脂固定在基材层表面。其创新性在于使用氮原子修饰二氧化钛，拓展了二氧化钛的可见光响应范围，具有良好的防指纹抗菌效果。但其表面水接触角在100°-110°之间，仍易被细菌黏附，可见光照射24小时后杀菌率仅为60％左右，效果有限。
构建双层或多重结构涂层可将抗菌、自清洁、高透光、高稳定性等几个重要特性整合至涂层中。例如，中国专利CN104845544A公开了一种双结构的抗菌抗眩抗刮保护膜及制备方法。其主要包括含有光固化清漆的抗菌抗刮花层与含有微米级硫酸钡与碳酸钡晶须胶体的抗眩处理层，以及附属粘接层、保护层与剥离层等。然而，由于抗菌抗刮花层并不直接暴露在表面，也无法释放杀菌剂，限制了其抗菌效果。
发明内容
本发明针对现有技术中各种抗菌薄膜的问题与不足，提供一种含多层涂层结构的抗菌薄膜，其整合光催化杀菌与超疏水自清洁功能，且具有良好的透光性与高度稳定性，可应用于各类电子设备触摸屏,降低设备接触表面的染菌率，防止病菌通过电子触摸屏传播引起交叉感染。本发明所涉及方法包括：对光学薄膜表面进行活化处理，在薄膜表面引入二氧化钛纳米颗粒，并对表面进行微纳米结构处理，最后对表面进行氟化处理，获得兼具光催化杀菌与超疏水防污性能的功能性涂层，可抑制细菌黏附生长，降低污染物吸附，同时具有良好的透光性能。
本发明的一方面提供了一种抗菌自清洁膜，所述抗菌自清洁膜包括：
薄膜基材；
二氧化钛交联层，位于在所述薄膜基材上；
氟化层，位于所述二氧化钛交联层上。
本领域技术人员可根据实际需要，选择薄膜基材的种类，所述薄膜基材选自光学薄膜中的至少一种。优选地，所述薄膜基材选自聚对苯二甲酸乙二醇酯(PET)薄膜、聚乙烯(PE)薄膜、聚丙烯(PP)薄膜、聚乙烯醇(PVA)薄膜、聚氟乙烯(PVF)薄膜、聚氯乙烯(PVC)薄膜、玻璃薄膜中的至少一种。
本领域技术人员可根据实际需要，可在0.01mm～0.5mm的范围内，选择薄膜基材的具体厚度。
在优选的实施方式中，所述二氧化钛交联层包括二氧化钛纳米颗粒。
优选地，所述抗菌自清洁膜在波长400～800nm可见光范围内的透光率>90％。
优选地，所述抗菌自清洁膜的水接触角≥149°。进一步优选地，所述抗菌自清洁膜的水接触角为149°～155°。
优选地，所述抗菌自清洁膜在光照条件下对革兰氏阳性菌和革兰氏阴性菌的杀菌率>90％。
本发明的另一方面提供了一种抗菌自清洁膜的制备方法，其特征在于，所述方法至少包括以下步骤：
1)将薄膜基材进行活化处理，得到表面含有羟基的薄膜基材；
2)在所述表面含有羟基的薄膜基材上形成二氧化钛交联层；
3)在所述二氧化钛交联层上形成氟化层。
在优选的实施方式中，所述步骤1)中的活化处理包括含氧气气氛下等离子处理、臭氧处理和酸处理中的至少一种。
在优选的实施方式中，所述步骤2)包括将含有纳米二氧化钛颗粒和硅酸酯的混合物A涂布于所述表面含有羟基的薄膜基材上并干燥；
在优选的实施方式中，所述硅酸酯选自具有式I所示化学式的化合物中的至少一种：
Figure BDA0001973610140000041
R1、R2、R3、R4独立地选自甲基、乙基、丙基或丁基；
所述纳米二氧化钛颗粒直径为10nm-100nm。
在优选的实施方式中，所述含有纳米二氧化钛颗粒和硅酸酯的混合物A中含，所述纳米二氧化钛颗粒与硅酸酯的重量比为0.1～200；
在优选的实施方式中，混合物A在薄膜基材上形成的二氧化钛交联层厚度为0.1-10μm。
在优选的实施方式中，所述步骤3)包括将含有氟硅烷的溶液B涂布于所述二氧化钛交联层上并干燥。
在优选的实施方式中，所述氟硅烷包括三甲氧基-1H,1H,2H,2H-十三氟正辛基硅烷、三甲氧基-1H,1H,2H,2H-十七氟癸基硅烷、三乙氧基氟硅烷、三乙氧基-1H,1H,2H,2H-十三氟正辛基硅烷、三乙氧基-1H,1H,2H,2H-十七氟癸基硅烷、三氯-1H,1H,2H,2H-十七氟癸基硅烷和三氯-1H,1H,2H,2H-十三氟正辛基硅烷中的至少一种。
混合物B在二氧化钛交联层上形成的氟硅烷层厚度为10-500nm。
本发明的又一方面，提供了抗菌自清洁膜或者根据上述任一方法制备的抗菌自清洁膜在电子显示屏、电子设备触摸屏以及具有触摸界面的设备中的至少一种应用。
本申请能产生的有益效果包括：
1)本发明通过光触媒催化杀菌，利用触摸屏工作时的光照持续产生杀菌物质，不因杀菌剂损耗而使杀菌效率下降；
2)本发明抗菌薄膜整合光催化杀菌与超疏水防污自清洁双重抗菌机制。光催化杀菌利用屏幕产生的光线，触发二氧化钛产生自由基，杀灭细菌；同时薄膜表面的超疏水特性降低表面污染，双重机制互补作用极大地提升薄膜的抗菌能力；
3)本发明的抗菌薄膜中含有二氧化钛，可吸收屏幕中的有害光线(主要为紫外线与短波蓝光)，保护使用者眼睛。
附图说明
图1为本发明提供的抗菌自清洁膜的构示意图。
附图标记说明：
101：基材；
201：二氧化钛纳米颗粒；
202：二氧化硅交联层；
203：氟化层。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
实施例1：抗菌自清洁膜的制备
(1)将厚度为0.1mm的聚酯(PET)薄膜表面通过氧气等离子体处理1-10分钟；
(2)配制涂层溶液A：依次将纳米二氧化钛颗粒、正硅酸四乙酯、25％氨水、乙醇、水等在室温下搅拌混合；
涂层溶液A各物质组分如下：
Figure BDA0001973610140000061
(3)将步骤(2)所得涂层溶液A均匀涂布在步骤(1)所得表面活化的PET薄膜上，60℃烘烤30分钟；
(4)配制涂层溶液B：依次将全氟硅氧烷偶联剂、乙醇、水在室温下搅拌混合；
涂层溶液B各物质组分如下：
Figure BDA0001973610140000062
(5)将步骤(4)所得涂层溶液B均匀涂布在步骤(3)所得表面修饰的PET薄膜上，60℃烘烤30分钟。
按照上述方法制备抗菌自清洁薄膜，所得抗菌自清洁薄膜的水接触角为152°±3°，在400nm-800nm的可见光范围内透光率>90％。
实施例1制得的抗菌自清洁膜样品的结构示意图如图1所示。接下来将对其杀菌性能、抗细菌黏附性能和涂层稳定性等方面进行测试。
实施例2：光照条件下薄膜杀菌性能测定
将实施例1中所得样品裁剪至1cm×1cm大小，放入24孔板中，对照组为未经表面修饰的同规格PET薄膜。将培养过夜的金黄色葡萄球菌(ATCC 25923，革兰氏阳性菌)用新鲜胰蛋白胨大豆肉汤培养基稀释至105CFU/ml，或将培养过夜的大肠杆菌(ATCC 25922，革兰氏阴性菌)用营养肉汤培养基稀释至105CFU/ml。取100μl上述菌液滴加至样品表面。将样品置于功率为5W的LED灯下方10cm处，室温条件下光照1小时。将样品放入5ml无菌PBS缓冲液中，超声清洗7分钟并振荡30s后，进行梯度稀释，用稀释液涂布琼脂平板进行细菌计数。杀菌率为实验样品的菌落总数与对照样品的菌落总数的比值(以百分数计)。对比对照组，实验样品对金黄色葡萄球菌和大肠杆菌的杀菌率分别为≥99.95％和≥95.00％。
对比例1：无光照条件下薄膜杀菌性能测定
测试方法参照实施例2，不同之处在于，将菌液加至样品表面后，样品用不透光的纸盒覆盖，室温放置1小时，再进行细菌计数。对比对照组，实验样品对金黄色葡萄球菌和大肠杆菌的杀菌率分别为15％和12％。
实施例3：涂层抗细菌黏附性能测定
将实施例1中所得样品裁剪至1cm×1cm大小，放入24孔板中，对照组为未经表面修饰的同规格PET薄膜。将培养过夜的金黄色葡萄球菌(ATCC 25923)菌液离心(2700rpm，10min)获得菌块，用无菌PBS缓冲液稀释至108CFU/ml，取1ml菌液加至各个放置样品的孔中。将样品置于功率为5W的LED灯下方10cm处，室温条件下光照4小时。样品用无菌PBS缓冲液清洗去除未黏附细菌，将样品放入5ml无菌PBS缓冲液中，超声清洗7分钟并振荡30s后，进行梯度稀释，用稀释液涂布琼脂平板进行细菌计数。对比对照组，实验样品表面的细菌黏附数减少率≥97％。
实施例4：涂层稳定性能测定
将实施例1中所得样品裁剪至1cm×10cm的长条，放置于玻璃板上，一端用夹子固定。使用消毒湿巾在薄膜表面向同一方向连续擦拭60次，结束后用去离子水冲洗，按照实施例2所述步骤用金黄色葡萄球菌(ATCC25923)进行杀菌性能测定实验。对比对照组，实验样品的杀菌率≥95％。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (10)

1.一种抗菌自清洁膜，其特征在于，所述抗菌自清洁膜包括：
薄膜基材；
二氧化钛交联层，位于在所述薄膜基材上；
氟化层，位于所述二氧化钛交联层上。
2.根据权利要求1所述的抗菌自清洁膜，其特征在于，所述抗菌自清洁膜在波长400～800nm可见光范围内的透光率>90％；
所述抗菌自清洁膜的水接触角≥149°。
3.根据权利要求1所述的抗菌自清洁膜，其特征在于，所述抗菌自清洁膜在光照条件下对革兰氏阳性菌和革兰氏阴性菌的杀菌率>90％。
4.一种抗菌自清洁膜的制备方法，其特征在于，所述方法至少包括以下步骤：
1)将薄膜基材进行活化处理，得到表面含有羟基的薄膜基材；
2)在所述表面含有羟基的薄膜基材上形成二氧化钛交联层；
3)在所述二氧化钛交联层上形成氟化层。
5.根据权利要求4所述的制备方法，其特征在于，所述步骤1)中的活化处理包括含氧气气氛下等离子处理、臭氧处理和酸处理中的至少一种。
6.根据权利要求4所述的制备方法，其特征在于，所述步骤2)包括将含有纳米二氧化钛颗粒和硅酸酯的混合物A涂布于所述表面含有羟基的薄膜基材上并干燥；
所述硅酸酯选自具有式I所示化学式的化合物中的至少一种：
Figure FDA0001973610130000021
R1、R2、R3、R4独立地选自甲基、乙基、丙基或丁基；
所述纳米二氧化钛颗粒直径为10nm-100nm。
7.根据权利要求6所述的制备方法，其特征在于，所述含有纳米二氧化钛颗粒和硅酸酯的混合物A中含，所述纳米二氧化钛颗粒与硅酸酯的重量比为0.1～200；
混合物A在薄膜基材上形成的二氧化钛交联层厚度为0.1～10μm。
8.根据权利要求4所述的制备方法，其特征在于，所述步骤3)包括将含有氟硅烷的溶液B涂布于所述二氧化钛交联层上并干燥。
9.根据权利要求8所述的制备方法，其特征在于，所述氟硅烷包括三甲氧基-1H,1H,2H,2H-十三氟正辛基硅烷、三甲氧基-1H,1H,2H,2H-十七氟癸基硅烷、三乙氧基氟硅烷、三乙氧基-1H,1H,2H,2H-十三氟正辛基硅烷、三乙氧基-1H,1H,2H,2H-十七氟癸基硅烷、三氯-1H,1H,2H,2H-十七氟癸基硅烷和三氯-1H,1H,2H,2H-十三氟正辛基硅烷中的至少一种；
混合物B在二氧化钛交联层上形成的氟硅烷层厚度为10-500nm。
10.根据权利要求1至3所述的抗菌自清洁膜或者根据权利要求4至9中任一项方法制备的抗菌自清洁膜在电子显示屏、电子设备触摸屏以及具有触摸界面的设备中的至少一种应用。
CN201910126016.XA 2019-02-20 2019-02-20 一种抗菌自清洁膜及其制备方法和应用 Active CN111040221B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910126016.XA CN111040221B (zh) 2019-02-20 2019-02-20 一种抗菌自清洁膜及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910126016.XA CN111040221B (zh) 2019-02-20 2019-02-20 一种抗菌自清洁膜及其制备方法和应用

Publications (2)

Publication Number Publication Date
CN111040221A true CN111040221A (zh) 2020-04-21
CN111040221B CN111040221B (zh) 2022-06-03

Family

ID=70231368

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910126016.XA Active CN111040221B (zh) 2019-02-20 2019-02-20 一种抗菌自清洁膜及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN111040221B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113025103A (zh) * 2021-03-16 2021-06-25 北京石油化工学院 一种多效抗菌、抗病毒膜层及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103740292A (zh) * 2013-12-25 2014-04-23 东莞市纳利光学材料有限公司 一种可自清洁的纳米涂层保护膜及其制备方法
CN106983917A (zh) * 2017-03-01 2017-07-28 淮阴工学院 一种抗菌‑超疏水聚合物涂层的制备方法
CN107236140A (zh) * 2017-06-22 2017-10-10 张家港康得新光电材料有限公司 抗菌膜、其制备方法及包括其的包装材料
CN108384302A (zh) * 2018-03-02 2018-08-10 合肥酷飞新材料科技有限公司 一种复合防污膜及其制备使用方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103740292A (zh) * 2013-12-25 2014-04-23 东莞市纳利光学材料有限公司 一种可自清洁的纳米涂层保护膜及其制备方法
CN106983917A (zh) * 2017-03-01 2017-07-28 淮阴工学院 一种抗菌‑超疏水聚合物涂层的制备方法
CN107236140A (zh) * 2017-06-22 2017-10-10 张家港康得新光电材料有限公司 抗菌膜、其制备方法及包括其的包装材料
CN108384302A (zh) * 2018-03-02 2018-08-10 合肥酷飞新材料科技有限公司 一种复合防污膜及其制备使用方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SWAGATA BANERJEE ET AL.: "Self-cleaning applications of TiO2 by photo-induced hydrophilicity and photocatalysis", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113025103A (zh) * 2021-03-16 2021-06-25 北京石油化工学院 一种多效抗菌、抗病毒膜层及其制备方法

Also Published As

Publication number Publication date
CN111040221B (zh) 2022-06-03

Similar Documents

Publication Publication Date Title
TWI540111B (zh) Ｃｕ、ＣｕＯ與ＣｕＯ奈米顆粒在玻璃表面與耐久塗層上的抗微生物作用
CA2965978C (en) Composition and method to form a self decontaminating surface
KR102164715B1 (ko) 항균점착필름의 제조방법
US9724440B2 (en) Environmental cleaning and antimicrobial lighting component and fixture
Lin et al. Photocatalytic and antibacterial properties of medical‐grade PVC material coated with TiO2 film
CN105565670B (zh) 一种陶瓷或搪瓷杀菌釉面材料及其制备方法及其应用
Page et al. Light-activated antibacterial screen protectors for mobile telephones and tablet computers
US20110045204A1 (en) Coating process and coated products
KR20140144865A (ko) 향균내지문 코팅 조성물, 그 피막, 그 코팅 방법, 및 그 코팅이 적용된 제품
CN111040221B (zh) 一种抗菌自清洁膜及其制备方法和应用
WO2023022368A1 (ko) 항균, 항바이러스 및 탈취 효과를 가진 항균막 및 그 제조방법
De Jong et al. Pre–post evaluation of effects of a titanium dioxide coating on environmental contamination of an intensive care unit: the TITANIC study
Ozkan et al. The antibacterial properties of light-activated polydimethylsiloxane containing crystal violet
Ismail et al. Self-cleaning application of mesoporous ZnO, TiO2 and Fe2O3 films with the accommodation of silver nanoparticles for antibacterial activity
JP3914982B2 (ja) 抗菌材料及びそれを用いた抗菌製品
CN111683692A (zh) 内墙面消毒的光催化方法和具有光催化性能的可清洗杀菌涂料的组合物
Talebian et al. The anti-adherence and bactericidal activity of sol–gel derived nickel oxide nanostructure films: solvent effect
WO2016122995A1 (en) Antibacterial composition of silver nanoparticles bonded to a dispersing agent
EP2843019A1 (en) Antibacterial hybrid layer operating against pathogenic bacterial strains, particularly against the bacterial strain MRSA, and a method for its preparation
TW201544763A (zh) 具有抗微生物／抗真菌板材及清淨空間能力之照明裝置
Akarsu et al. Light-activated hybrid organic/inorganic antimicrobial coatings
EP3491078A1 (en) Contaminant-activated photocatalysis
CN111742934A (zh) 一种光触媒空气杀菌消毒剂及其应用
CN210176775U (zh) 一种透明抗菌涂层及包含该涂层的抗菌玻璃
Lin et al. Coating of medical-grade PVC material with ZnO for antibacterial application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant