CN108949054B - Transparent antibacterial window film - Google Patents
Transparent antibacterial window film Download PDFInfo
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- CN108949054B CN108949054B CN201810868619.2A CN201810868619A CN108949054B CN 108949054 B CN108949054 B CN 108949054B CN 201810868619 A CN201810868619 A CN 201810868619A CN 108949054 B CN108949054 B CN 108949054B
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- coating
- bacteriostatic
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- antibacterial
- acrylic adhesive
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 91
- 239000011248 coating agent Substances 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000010410 layer Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004642 Polyimide Substances 0.000 claims abstract description 28
- 239000002985 plastic film Substances 0.000 claims abstract description 28
- 229920006255 plastic film Polymers 0.000 claims abstract description 28
- 229920003055 poly(ester-imide) Polymers 0.000 claims abstract description 28
- 229920001721 polyimide Polymers 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 20
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000003385 bacteriostatic effect Effects 0.000 claims description 73
- 239000003522 acrylic cement Substances 0.000 claims description 42
- 239000000022 bacteriostatic agent Substances 0.000 claims description 37
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical group OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 7
- 230000002045 lasting effect Effects 0.000 abstract description 4
- 239000012790 adhesive layer Substances 0.000 abstract description 3
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 29
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- -1 acylanilines Chemical class 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical group NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical group [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000656 anti-yeast Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical class CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- 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
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a transparent antibacterial window film, which consists of an antibacterial coating, a transparent polyester or polyimide plastic film substrate, an acrylic acid adhesive layer and a release film, wherein all the layers are compounded into a whole; the anti-bacterial coating is formed by coating an anti-bacterial composition on the outer side surface of the transparent polyester or polyimide plastic film base material, which is provided with the acrylic coating, and performing ultraviolet curing under a high-pressure mercury lamp after volatilizing a solvent at the low temperature of 50-70 ℃. In the transparent antibacterial window film provided by the invention, the antibacterial coating is cured by ultraviolet light without high-temperature baking and curing, so that the defect of poor thermal stability of an organic antibacterial agent is avoided, and the antibacterial coating with the thickness of 4-12 mu m can be formed to provide a lasting antibacterial effect and have excellent wear-resistant and anti-fouling effects.
Description
Technical Field
The invention relates to a window film suitable for being adhered to the surface of window glass of a building or window glass of an automobile, in particular to a transparent bacteriostatic window film with a bacteriostatic coating.
Background
Based on the requirements of heat insulation, explosion prevention, ultraviolet protection, fog prevention and the like, window films with various functions, such as heat insulation window films, explosion prevention window films, ultraviolet protection window films, fog prevention window films and the like, are generally adhered on the surfaces of door and window glass of vehicles and buildings. For the interior or indoor environment of a vehicle, once the window film is bred with bacteria, great inconvenience is brought to healthy life, and under normal conditions, general people can not pay attention to the problem that whether the window film has the bacteria or not, so that the breeding of the bacteria on the window film can form a pollution source which is difficult to find, and great pollution hidden trouble is realized. The bacteriostatic coating is coated on the surface of the window film, so that the growth of bacteria on the window film can be inhibited, and the propagation of the bacteria can be effectively prevented.
The common bacteriostatic coating is formed by adding bacteriostatic agent on the basis of common coating and coating the bacteriostatic agent on the surface of a window film for curing. The bacteriostatic agent is used as a functional auxiliary agent to be dispersed in a coating system and exists in the coating after being cured. The bacteriostatic agent can be organic bacteriostatic agent or inorganic bacteriostatic agent. The bacteriostatic agent serving as the functional auxiliary agent has a common defect that the binding force with other components of common coatings is not enough, particularly, inorganic bacteriostatic agents can migrate to the surface of a coating along with the lapse of time, and the bacteriostatic agent is lost by wiping the surface of the coating, so that the bacteriostatic ability is attenuated, and even the bacteriostatic ability is lost.
The organic bacteriostatic agent is divided into two types of organic small-molecular bacteriostatic agents and high-molecular bacteriostatic agents, which are various, and mainly comprises vanillin or ethyl vanillin compounds, acylanilines, imidazoles, thiazoles, isothiazolone derivatives, quaternary ammonium salts, quaternary phosphonium salts, biguanidine compounds, phenols and the like, and also comprises chitin, mustard, castor oil, horseradish and other natural bacteriostatic agents. The organic small molecular bacteriostatic agent is easy to volatilize, has poor chemical stability, poor compatibility with base materials and difficult dispersion in the base materials. Another significant disadvantage of organic bacteriostats is their poor thermal stability and unsuitability for high temperature thermal curing applications.
The inorganic bacteriostatic agent is prepared by fixing metals (or ions thereof) such as silver, copper, zinc and the like on the surface of porous materials such as fluorite, silica gel and the like by utilizing the bacteriostatic ability of the metals such as silver, copper, zinc and the like and corresponding metal ions through methods such as physical adsorption, ion exchange and the like, and then adding the bacteriostatic agent into a coating system, and of course, metal powder such as silver, copper, zinc and the like and corresponding inorganic salt powder can also be directly added into the coating. The bacteriostatic agent is usually used for silver-carrying zeolite, silver-carrying zinc zeolite, etc., and the main bacteriostatic factor is silver ion or silver. The other inorganic bacteriostat, such as nano titanium dioxide, can be directly added into the coating system to play a role in bacteriostasis. The inorganic bacteriostatic agent has the advantages of good heat stability, wide spectrum bacteriostasis, high bacteriostasis efficiency and difficult generation of drug resistance, and can be applied to baking type coatings; the disadvantages are that silver ions or silver is easy to discolor and is not suitable for light-colored paint; the nano titanium dioxide can exert bacteriostatic activity only by illumination, and atomic oxygen decomposed under illumination can decompose coating resin to cause the deterioration of coating performance; another significant drawback is the aforementioned migration to the surface of the coating over time, attenuation of the bacteriostatic ability and even loss of the bacteriostatic ability.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a transparent bacteriostatic window film to reduce or avoid the aforementioned problems.
Specifically, the invention provides a transparent bacteriostatic window film, wherein a bacteriostatic coating is formed by coating a bacteriostatic composition containing an organic bacteriostatic agent on the surface of the window film, the bacteriostatic coating can be cured without high-temperature baking, the defect of poor thermal stability of the organic bacteriostatic agent is avoided, and the formed bacteriostatic coating has a lasting bacteriostatic effect and excellent wear-resistant and anti-fouling effects.
In order to solve the technical problem, the invention provides a transparent antibacterial window film which is composed of an antibacterial coating, a transparent polyester or polyimide plastic film substrate, an acrylic acid adhesive layer and a release film, wherein all the layers are compounded into a whole; the anti-bacterial coating is formed by coating an anti-bacterial composition on the outer side surface of the transparent polyester or polyimide plastic film base material with the acrylic coating, volatilizing a solvent at the low temperature of 50-70 ℃ and then carrying out ultraviolet curing under a high-pressure mercury lamp; the antibacterial composition is formed by uniformly mixing the following components at normal temperature, wherein the ratio of each component is as follows: high functional group monomer: 10 to 35 weight percent; low functional group monomer: 5 to 25 weight percent; ethyl acetate: 5 to 15 weight percent; butyl acetate: 5 to 15 weight percent; isopropyl alcohol: 5 to 15 weight percent; butanone: 5 to 10 weight percent; photoinitiator (2): 1 to 5 weight percent; leveling agent: 1 to 3 weight percent; wear-resistant auxiliary agent: 0.1 to 1 weight percent; a bacteriostatic agent: 1 to 5 weight percent; the sum of the components is 100wt%; the bacteriostatic agent is a bacteriostatic agent with UV reactive groups, which is sold by three specialized chemical industries of Changzhou and has the name of ST-382.
Preferably, the photoinitiator is an alpha-hydroxyketone.
Preferably, the high functional monomer is Dipentaerythritol Pentahexaacrylate (DPHA).
Preferably, the low functional monomer is nonylphenol polyoxyethylene ether acrylate.
Preferably, the leveling agent is a BYK-351 leveling agent available from Bick chemical, germany.
Preferably, the abrasion-resistant auxiliary agent is a fluorine-containing auxiliary agent sold by Sanspeciality chemical engineering Co., ltd under the name 1203 HY.
Preferably, the acrylic adhesive layer is formed by coating an acrylic adhesive mixture on the surface of a transparent polyester or polyimide plastic film substrate, standing at 90-150 ℃ for 10-150 seconds and then curing, wherein the acrylic adhesive mixture is prepared by mixing, by mass, 4-50: 0.003-0.2: 1 to 15: 2-35 acrylic adhesive: curing agent: 4-methyl-2-pentanone: butanone, namely mixing butanone, 4-methyl-2-pentanone and acrylic acid adhesive at the ambient temperature of 18-28 ℃, stirring for 15-20 minutes, adding a curing agent, and stirring for 20-30 minutes to obtain the adhesive, wherein the viscosity of the adhesive is 80-300 centipoises; the release film is compounded on the outer surface of the acrylic adhesive layer.
Preferably, the acrylic adhesive is SAA1451 produced by SAN 'AN aerospace SanWao chemical Co., ltd, and has a solid content of 40-45% by mass, and the curing agent is SAC11 produced by SAN' AN aerospace SanWao chemical Co., ltd, and has a solid content of 60% by mass, or the acrylic adhesive is SAA1401 produced by SAN 'AN aerospace SanWao chemical Co., ltd, and has a solid content of 40-45% by mass, and the curing agent is SAC12 produced by SAN' AN aerospace SanWao chemical Co., ltd, and has a solid content of 5% by mass.
Preferably, the thickness of the transparent bacteriostatic window film is 79-251 μm, wherein the thickness of the bacteriostatic coating is 4-12 μm; the thickness of the transparent polyester or polyimide plastic film base material is 50-175 μm; the thickness of the acrylic adhesive layer is 6-25 mu m; the thickness of the release film is 19-39 μm.
In the transparent antibacterial window film provided by the invention, the antibacterial coating is cured by ultraviolet light without being baked and cured at high temperature, so that the defect of poor thermal stability of an organic antibacterial agent is overcome, and the formed antibacterial coating has a lasting antibacterial effect and excellent wear-resistant and anti-fouling effects.
Drawings
The drawings are only for purposes of illustrating and explaining the present invention and are not to be construed as limiting the scope of the present invention. Wherein,
fig. 1 shows a schematic view of a transparent bacteriostatic window film according to an embodiment of the invention.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, embodiments of the present invention will now be described with reference to the accompanying drawings. Wherein like parts are given like reference numerals. The starting materials used in the examples are, unless otherwise indicated, commercially available commercial products which are commercially available from commercial sources.
As described in the background section, in view of the defect that the conventional bacteriostatic coating is prone to discoloration due to the use of an inorganic bacteriostatic agent, the application of the bacteriostatic coating to a window film is easy to reduce the use appearance, so that the invention provides a transparent bacteriostatic window film with a bacteriostatic composition, wherein the bacteriostatic composition contains an organic bacteriostatic agent, and in order to avoid the defect of poor thermal stability of the organic bacteriostatic agent, the bacteriostatic composition is cured by means of UV irradiation at a lower temperature, so that a bacteriostatic coating with a thickness of 4-12 μm can be formed to provide a lasting bacteriostatic effect, and the bacteriostatic coating has excellent wear resistance and stain resistance.
The transparent bacteriostatic window film is shown in figure 1 and consists of a bacteriostatic coating 1, a transparent polyester or polyimide plastic film substrate 2, an acrylic acid adhesive layer 3 and a release film 4, wherein the layers are compounded into a whole. An acryl coating layer is previously formed on the outer side surface of the transparent polyester or polyimide plastic film substrate 2, and the other side surface (inner side surface) thereof is not provided with the acryl coating layer. The thickness of the transparent bacteriostatic window film is 79-251 mu m, wherein the thickness of the bacteriostatic coating 1 is 4-12 mu m; the thickness of the transparent polyester or polyimide plastic film base material 2 is 50 to 175 μm; the thickness of the acrylic adhesive layer 3 is 6 to 25 μm; the thickness of the release film 4 is 19 to 39 μm.
The thickness of the bacteriostatic coating 1 of the transparent bacteriostatic window film can reach 4-12 mu m, which is far more than the thickness of a common coating with the general thickness of 1-2 mu m, so that the defects of full-surface crystal points and unobvious bacteriostatic effect caused by too thin coating thickness can be avoided. In addition, the transparent polyester or polyimide plastic film substrate 2 of the invention preferably uses a film material with an acrylic coating, such as a film substrate with a name of SX185 produced by jiangsu color plastic ltd, when the surface of the substrate is produced, the acrylic coating is coated on the surface of PET, and the acrylic coating thereon can form a chemical bond with the bacteriostatic coating 1 of the invention to be firmly combined, so that the surface of the film substrate 2 can form a coating with a thickness of 4-12 μm, and the problem that the conventional coating is too thick and is easy to fall off can be overcome.
In a specific embodiment, the bacteriostatic coating 1 is formed by curing the following bacteriostatic composition, wherein the bacteriostatic composition is a composition formed by uniformly mixing the following components at normal temperature, and the mixture ratio of the components is as follows:
the sum of the components is 100wt%; the bacteriostatic agent is an organic bacteriostatic agent sold by three speciality chemical industries of Hezhou, inc. under the name of ST-382, and has remarkable antibacterial, antifungal, and anti-yeast effects. The official website of Changzhou three speciality chemical Limited is: http:// www.sunttochemical.com.
In another embodiment, the photoinitiator is an alpha-hydroxy ketone, which may be a photoinitiator manufactured by BASF-IRGACURE 184, BASF, germany. The photoinitiator can be rapidly cured with the bacteriostatic agent under the irradiation of an ultraviolet mercury lamp, so that the damage of high-temperature curing to the organic bacteriostatic agent is avoided. For example, the bacteriostatic composition of the invention is coated on the surface of a window film to form a coating with the thickness of 12 microns, and the coating can be subjected to solvent volatilization at a low temperature of 50-70 ℃ and then ultraviolet curing under a high-pressure mercury lamp to form the bacteriostatic coating.
Further, the high functional monomer may be dipentaerythritol pentahexaacrylate (e.g., DPHA available under the names M-400 or M-402 from Dow chemical Co., ltd., east Asia, zhang). The low functional monomer may be nonylphenol polyoxyethylene ether acrylate (e.g., M-113 difunctional monomer available from denai chemicals ltd, tokyo, york). Chemistry of Di-ai-Sheng in Tokyo the official website of limited company is: http:// www.tdz.cn/.
The high-functional group monomer and the low-functional group monomer can be purchased from Dietyoh of east Asia of Zhang Home, wherein the high-functional group monomer is DPHA and the six-functional group monomer has the main functions of: the fullness and the wear resistance are increased, and the shrinkage rate is low; the low functional group monomer is a difunctional monomer and has the main functions of: the curing speed is high, and the adhesion to materials is increased; the coating has high hardness, wear resistance and fullness under the condition of ensuring good adhesive force.
In addition, the leveling agent may be a BYK-351 leveling agent available from Bick chemical company, germany. For example, various supply information of the BYK-351 leveling agent can be searched by Baidu search, and the supply information can be directly purchased through a website or other sale channels by the technical personnel in the field.
The wear-resistant additive is a fluorine-containing additive which is sold by Santa chemical Limited company of Changzhou (http:// www.sunttochemical.com) and is named 1203HY, and has very excellent slipping property, stain resistance and wear resistance. The fluorine-containing components in the auxiliary agent can perform cross-linking reaction with the coating, so that the coating can keep high wear resistance and stain resistance for a long time.
Example 1 preparation of bacteriostatic compositions A-C
(1) Formulation of
The specific formulation is shown in table 1.
TABLE 1
(2) Preparation of
Weighing the components according to the formula of the formula shown in the table 1, putting the components into a container, stirring and mixing the components uniformly at normal temperature to prepare the antibacterial compositions A to C respectively, and packaging the antibacterial compositions A to C.
EXAMPLE 2 preparation of a transparent bacteriostatic Window film
The specific operation is as follows:
(A) Preparing the raw materials
(1) Preparing a transparent polyester or polyimide plastic film substrate with the thickness of 50 mu m, such as a film substrate with the name of SX185 produced by Jiangsu double star color plastic Co., ltd, wherein the surface of the SX185 film substrate is provided with an acrylic coating on one side and is not provided with the acrylic coating on the other side when the film substrate is delivered from a factory; and a release film 4 having a thickness of 19 μm.
(2) The bacteriostatic composition a prepared in example 1 was prepared.
(3) A mixed material for forming the acrylic adhesive layer 3 was prepared.
According to the acrylic acid adhesive: curing agent: 4-methyl-2-pentanone: the mass ratio of the butanone is 50:0.2:15:35 preparing the above components.
Wherein the acrylic adhesive is SAA1451 produced by SAN 'AN aerospace Sanwo chemical Co., ltd, the solid content is 40-45% by mass, the curing agent is SAC11 produced by SAN' AN aerospace Sanwo chemical Co., ltd, the solid content is 60% by mass, and the 4-methyl-2-pentanone and butanone can be obtained from Changzhou Source chemical Co., ltd. Or the acrylic adhesive is SAA1401 produced by the three-Watson chemical company of Sian space, the solid content is 40-45% by mass, the curing agent is SAC12 produced by the three-Watson chemical company of Sian space, and the solid content is 5% by mass.
The raw materials can be replaced by equivalent products of different production plants.
At the ambient temperature of 18-28 ℃, butanone, 4-methyl-2-pentanone and acrylic acid adhesive are mixed and stirred for 15-20 minutes, curing agent is added and stirred for 20-30 minutes, and the mixture is preserved for later use, wherein the viscosity of the mixture is 80-300 centipoises.
(B) Preparation of transparent antibacterial window film
One side of a transparent polyester or polyimide plastic film substrate 2 with an acrylic coating is used as an outer side surface, after an antibacterial composition A forming the antibacterial coating 1 is coated on the outer side surface, the antibacterial coating 1 is formed by ultraviolet curing under a high-pressure mercury lamp after a solvent is volatilized at a low temperature of 50-70 ℃.
After coating the mixed material forming the acrylic adhesive layer 3 on the other side surface (the inner side surface without the acrylic coating) of the transparent polyester or polyimide plastic film substrate 2, standing at the temperature of 80-130 ℃ for 10-120 seconds, curing to form the acrylic adhesive layer 3, and then compounding the release film 4 on the outer surface of the acrylic adhesive layer 3, thereby obtaining the transparent bacteriostatic window film (as shown in figure 1) with all layers compounded into a whole.
Wherein the thickness of the bacteriostatic coating 1 is 8 μm; the thickness of the acrylic adhesive layer 3 is 15 μm; the thickness of the transparent bacteriostatic window film is 92 mu m
When the bacteriostatic composition forming the bacteriostatic agent coating layer 1 and the mixed material forming the acrylic adhesive layer 3 are applied, spray coating, knife coating, or comma coating may be used.
EXAMPLE 3 preparation of transparent bacteriostatic Window film
The specific operation is as follows:
(A) Preparing the raw materials
(1) Preparing a transparent polyester or polyimide plastic film substrate with the thickness of 175 mu m, such as a film substrate with the name of SX185 produced by Jiangsu double star color plastic Co., ltd, wherein the surface of the SX185 film substrate is provided with an acrylic coating on one side and is not provided with the acrylic coating on the other side when the film substrate is delivered from a factory; and a release film 4 having a thickness of 39 μm.
(2) The bacteriostatic composition B prepared in example 1 was prepared.
(3) A mixed material for forming the acrylic adhesive layer 3 was prepared.
According to the acrylic acid adhesive: curing agent: 4-methyl-2-pentanone: the mass ratio of the butanone is 4:0.003:1:2 the above components were prepared.
Wherein the acrylic adhesive is SAA1451 produced by SAN 'AN aerospace Sanwo chemical Co., ltd, the solid content is 40-45% by mass, the curing agent is SAC11 produced by SAN' AN aerospace Sanwo chemical Co., ltd, the solid content is 60% by mass, and the 4-methyl-2-pentanone and butanone can be obtained from Changzhou Source chemical Co., ltd. Or the acrylic adhesive is SAA1401 produced by the three-Watson chemical company of Sian space, the solid content is 40-45% by mass, the curing agent is SAC12 produced by the three-Watson chemical company of Sian space, and the solid content is 5% by mass.
The raw materials can be replaced by equivalent products of different production plants.
At the ambient temperature of 18-28 ℃, butanone, 4-methyl-2-pentanone and acrylic acid adhesive are mixed and stirred for 15-20 minutes, curing agent is added and stirred for 20-30 minutes, and the mixture is preserved for later use, wherein the viscosity of the mixture is 80-300 centipoises.
(B) Preparation of transparent antibacterial window film
One side of a transparent polyester or polyimide plastic film substrate 2 with an acrylic coating is used as an outer side surface, and after an antibacterial composition B forming a bacteriostatic agent coating 1 is coated on the outer side surface, the transparent polyester or polyimide plastic film substrate is subjected to ultraviolet curing under a high-pressure mercury lamp after a solvent is volatilized at a low temperature of 50-70 ℃ to form the bacteriostatic coating 1.
After the mixed material for forming the acrylic adhesive layer 3 is coated on the other side surface (the inner side surface without the acrylic coating) of the transparent polyester or polyimide plastic film substrate 2, the acrylic adhesive layer 3 is formed by curing after the mixture is placed for 10 to 120 seconds at the temperature of 80 to 150 ℃, and then the release film 4 is compounded on the outer surface of the acrylic adhesive layer 3, so that the transparent bacteriostatic window film (shown in the attached figure 1) with all layers compounded into a whole is obtained.
Wherein the thickness of the bacteriostatic coating 1 is 12 μm; the thickness of the acrylic adhesive layer 3 is 25 μm; the thickness of the transparent bacteriostatic window film is 251 mu m.
When the bacteriostatic composition forming the bacteriostatic agent coating layer 1 and the mixed material forming the acrylic adhesive layer 3 are applied, spray coating, knife coating, or comma coating may be used.
EXAMPLE 4 preparation of transparent bacteriostatic Window film
The specific operation is as follows:
(A) Preparing the raw materials
(1) Preparing a transparent polyester or polyimide plastic film substrate with the thickness of 120 mu m, such as a film substrate with the name of SX185 produced by Jiangsu double star color plastic Co., ltd, wherein the surface of the SX185 film substrate is provided with an acrylic coating on one side and is not provided with the acrylic coating on the other side when the film substrate is delivered from a factory; and a release film 4 having a thickness of 23 μm.
(2) The bacteriostatic composition C prepared in example 1 was prepared.
(3) A mixed material for forming the acrylic adhesive layer 3 was prepared.
According to the acrylic acid adhesive: curing agent: 4-methyl-2-pentanone: the mass ratio of the butanone is 25:0.1:8:20 preparing the above components.
Wherein the acrylic adhesive is SAA1451 produced by SAN 'AN aerospace Sanwo chemical Co., ltd, the solid content is 40-45% by mass, the curing agent is SAC11 produced by SAN' AN aerospace Sanwo chemical Co., ltd, the solid content is 60% by mass, and the 4-methyl-2-pentanone and butanone can be obtained from Changzhou Source chemical Co., ltd. Or the acrylic adhesive is SAA1401 produced by the three-Watson chemical company of Sian space, the solid content is 40-45% by mass, the curing agent is SAC12 produced by the three-Watson chemical company of Sian space, and the solid content is 5% by mass.
The raw materials can be replaced by equivalent products of different production plants.
At the ambient temperature of 18-28 ℃, butanone, 4-methyl-2-pentanone and acrylic acid adhesive are mixed and stirred for 15-20 minutes, curing agent is added and stirred for 20-30 minutes, and the mixture is preserved for later use, wherein the viscosity of the mixture is 80-300 centipoises.
(B) Preparation of transparent bacteriostatic window film
One side of a transparent polyester or polyimide plastic film substrate 2 with an acrylic coating is used as the outer side surface, after an antibacterial composition C forming an antibacterial agent coating 1 is coated on the transparent polyester or polyimide plastic film substrate, the transparent polyester or polyimide plastic film substrate is subjected to ultraviolet curing under a high-pressure mercury lamp after a solvent is volatilized at a low temperature of 50-70 ℃ to form the antibacterial coating 1.
After the mixed material for forming the acrylic adhesive layer 3 is coated on the other side surface (the inner side surface without the acrylic coating) of the transparent polyester or polyimide plastic film substrate 2, the acrylic adhesive layer 3 is formed by curing after the mixed material is placed for 10 to 120 seconds at the temperature of 80 to 130 ℃, and then the release film 4 is compounded on the outer surface of the acrylic adhesive layer 3, so that the transparent bacteriostatic window film (shown in the attached figure 1) with all layers compounded into a whole is obtained.
Wherein the thickness of the bacteriostatic agent coating 1 is 4 μm; the thickness of the acrylic adhesive layer 3 is 6 μm; the thickness of the transparent bacteriostatic window film is 153 μm.
When the bacteriostatic composition forming the bacteriostatic coating 1 and the mixed material forming the acrylic adhesive layer 3 are applied, the spray coating, the knife coating, or the comma coating may be used.
Example 5 detection of Performance of transparent bacteriostatic Window films
The bacteriostatic coatings prepared in examples 2 to 4 were examined using Lambda950 manufactured by Perkinelmer, QUV manufactured by Q-Lab, USA, etc. (see tables 2 to 3).
Table 2: performance index
| Adhesion force | Grid-scribing method 1mm x 1mm NICIBAN adhesive tape | 100/100 |
| Hardness of pencil | Mitsubishi-UNI pencil, 45 degree angle, 500 g load | 2-3H |
| Optical Properties | GBT 29061-2012 | By passing |
| Weather resistance | QUV 500 hours delta Eab is less than or equal to 3 | By passing |
| Bacteriostatic activity | JIS Z 2801:2000 | By passing |
The invention has the technical effects that: the test article was tested for bacteriostatic activity according to the test methods of JIS Z2801, 2000< bacteriostatic processed articles-bacteriostatic activity test method, bacteriostatic effect >5.2 plastic articles, and the like.
TABLE 3 measurement results of the number of bacteria grown on the surface of the sample film
The results of the experiment on the persistence of the antibacterial effect are as follows:
the water resistance test method comprises the following steps: antibacterial effect persistence experimental method for antibacterial processed products formulated by Japan antibacterial product technology Association
Light resistance test method: antibacterial effect persistence experimental method of antibacterial processed product formulated by Japan antibacterial product technology Association
It should be appreciated by those of skill in the art that while the present invention has been described in terms of several embodiments, not every embodiment includes only a single embodiment. The description is given for clearness of understanding only, and it is to be understood that all matters in the embodiments are to be interpreted as including technical equivalents which are related to the embodiments and which are combined with each other to illustrate the scope of the present invention.
The above description is only an exemplary embodiment of the present invention, and is not intended to limit the scope of the present invention. Any equivalent alterations, modifications and combinations can be made by those skilled in the art without departing from the spirit and principles of the invention.
Claims (4)
1. A transparent bacteriostatic window film consists of a bacteriostatic coating (1), a transparent polyester or polyimide plastic film substrate (2), an acrylic adhesive layer (3) and a release film (4), wherein all the layers are compounded into a whole; the transparent polyester or polyimide plastic film is characterized in that an acrylic coating is formed on the outer side surface of the transparent polyester or polyimide plastic film base material (2) in advance; the antibacterial coating (1) is formed by coating the antibacterial composition on the outer side surface of the transparent polyester or polyimide plastic film base material (2) with the acrylic coating, volatilizing a solvent at 50-70 ℃, and then performing ultraviolet curing under a high-pressure mercury lamp; the antibacterial composition is formed by uniformly mixing the following components at normal temperature, wherein the ratio of each component is as follows: high functional group monomer: 10 to 35wt%; low functional group monomer: 5 to 25wt%; ethyl acetate: 5 to 15wt percent; butyl acetate: 5 to 15wt percent; isopropyl alcohol: 5 to 15wt percent; butanone: 5 to 10wt%; photoinitiator (2): 1 to 5wt%; leveling agent: 1 to 3wt%; wear-resistant auxiliary agent: 0.1 to 1wt%; bacteriostatic agent: 1 to 5wt%; the sum of the components is 100wt%; the bacteriostatic agent is a bacteriostatic agent with UV reaction groups, which is sold by three speciality chemical industries, inc. of Heizhou and is named as ST-382; the photoinitiator is alpha-hydroxy ketone; the high-functional group monomer is dipentaerythritol pentahexaacrylate; the low-functional group monomer is nonylphenol polyoxyethylene ether acrylate; the leveling agent is a BYK-351 leveling agent which is available from German Bick chemical company; the wear-resistant auxiliary agent is a fluorine-containing auxiliary agent sold by three specialized chemical industries, inc. of Heizhou under the name 1203 HY; the thickness of the antibacterial coating (1) is 4-12 μm.
2. The window film according to claim 1, wherein the acrylic adhesive layer (3) is formed by coating an acrylic adhesive mixture on the surface of the transparent polyester or polyimide plastic film substrate (2) and curing the acrylic adhesive mixture after standing at a temperature of 90 ℃ to 150 ℃ for 10 to 150 seconds, wherein the acrylic adhesive mixture is prepared by mixing, by mass, 4 to 50: 0.003-0.2: 1 to 15: 2-35 acrylic adhesive: curing agent: 4-methyl-2-pentanone: butanone; the release film (4) is compounded on the outer surface of the acrylic adhesive layer (3).
3. The window film according to claim 2, wherein the acrylic adhesive is SAA1401 produced by seian spaceflight sumiwo chemical limited having a solid content of 40% to 45% by mass, and the curing agent is SAC12 produced by seian spaceflight sumiwo chemical limited having a solid content of 5% by mass.
4. The window film of claim 2, wherein the transparent bacteriostatic window film has a thickness of 79 to 251 μm, wherein the transparent polyester or polyimide plastic film substrate (2) has a thickness of 50 to 175 μm; the thickness of the acrylic adhesive layer (3) is 6-25 mu m; the thickness of the release film (4) is 19-39 μm.
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| CN113604165A (en) * | 2021-08-30 | 2021-11-05 | 广东安可科技有限公司 | Anti-fouling and anti-explosion film for bathroom and preparation method thereof |
| CN115181311B (en) * | 2022-08-01 | 2024-01-09 | 江苏双星彩塑新材料股份有限公司 | Antibacterial inner suspension film |
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