Film having excellent Anti-fogging effect and durability, and manufacturing method thereof

Abstract

The objective of the present invention is to provide a film having an excellent anti-fogging effect and a manufacturing method thereof. More specifically, the present invention relates to the manufacture of a film having a long-term anti-fogging effect and high chemical adhesion by photoreaction with thiol formed on a glass substrate. By developing a polymer capable of photoreaction with thiol while having an anti-fogging effect, a polymer film that can last for a long period and exhibits high chemical adhesion with glass can be developed, and can be usefully used in related industries.

Description

Film with excellent anti-fogging effect and durability and method for manufacturing the same

[0001] The purpose of the present invention is to provide a film having excellent anti-fogging effect and durability and a method for producing the same, and more specifically, to produce a film having a long-term anti-fogging effect and high chemical adhesion by photoreacting with thiol formed on various substrates (glass, metal, polymer).

[0002] Fogging occurs when the surrounding environment is warmer than the object, causing the surrounding water vapor to condense on the object's surface, forming tiny water droplets. Fogging on car windows, eyeglasses, and other surfaces reduces visibility and can cause malfunctions in various sensors, significantly increasing the risk of accidents.

[0003] Therefore, research on preventing fogging has been ongoing for a long time. Conventional anti-fogging coatings primarily used thermosetting coatings utilizing amphoteric surfactants developed by Kao Soap of Japan in the 1980s. However, thermosetting coatings have a very short lifespan of less than three months, and their anti-fogging properties are lost when washed with solvents such as alcohol. Furthermore, the properties of thermosetting coatings make them unsuitable for application to polycarbonate and polyacrylic substrates.

[0004] Fogging occurs when temperature differences between surfaces cause the formation of microscopic water droplets, which interact with light, blurring objects or limiting visibility. To address this, technologies are needed to control the interaction between the surface and water. Typically, surfaces are treated to be hydrophilic or hydrophobic, controlling their affinity for moisture and preventing fogging.

[0005] For example, fogging on a car's windshield can obstruct the driver's view, making it difficult to clearly perceive road conditions. This obstruction can be particularly severe at night or in rainy weather. Furthermore, poor visibility can lead to the following accidents:

[0006] Fog can delay a driver's reaction time if they cannot properly read road signs or signals, and when driving at night, fog can further impair vision due to headlights or reflections.

[0007] Additionally, fogging can worsen in inclement weather, such as rain, snow, or fog, significantly impeding driver visibility. Furthermore, drivers may need to take additional steps, such as cleaning windows or adjusting the air conditioning, to continuously remove fogging.

[0008] In order to solve these problems, the inventors of the present invention developed a film having excellent anti-fogging effect and long-lasting properties, and synthesized poly(trimethyl methacrylate) ammonium chloride (PTMAC) and poly(allyl methacrylate) (PAMA) to produce a film, thereby completing the present invention by producing a film having excellent anti-fogging performance and high long-lasting properties.

[0009] An object of the present invention is to provide an anti-fogging film comprising an ionic polymer; an allylic polymer; a crosslinking agent; and a photoinitiator.

[0010] In addition, an object of the present invention is to provide a method for manufacturing an anti-fogging film, comprising the steps of: synthesizing an ionic polymer and an allylic polymer by a free radical polymerization method; and adding a crosslinking agent and a photoinitiator to the synthesized composite and crosslinking them with ultraviolet rays.

[0011] In addition, an object of the present invention is to provide a thiolated substrate; an anti-fog film on one side thereof; and an anti-fog plate bonded thereto.

[0012] The present invention provides an anti-fogging film comprising an ionic polymer; an allyl polymer; a crosslinking agent; and a photoinitiator.

[0013] In addition, the present invention provides a method for manufacturing an anti-fogging film, comprising the steps of: synthesizing an ionic polymer and an allylic polymer using a free radical polymerization method; and adding a crosslinking agent and a photoinitiator to the synthesized composite and crosslinking them with ultraviolet rays.

[0014] In addition, the present invention provides a thiolated substrate; an anti-fog film as described above on one side; and an anti-fog plate adhered thereto.

[0015] By developing a polymer that has a photoreactive property with thiol and has a Kim Seorim prevention effect, a polymer film that can be maintained for a long time and exhibits high chemical adhesion to a substrate can be developed, which can be usefully used in related businesses.

[0016] FIG. 1 is a diagram showing the structural formula of a copolymer of trimethyl methacrylate ammonium chloride and allyl methacrylate according to one embodiment of the present invention.

[0017] FIG. 2 is a diagram showing, in one embodiment of the present invention, an increase in transmittance among the effects of the anti-fogging film of the present invention.

[0018] FIG. 3 is a diagram showing, in one embodiment of the present invention, an increase in absorbency among the effects of the anti-fogging film of the present invention.

[0019] FIG. 4 is a diagram showing a strong covalent bonding process through a double bond and click reaction of the anti-fogging film of the present invention on a thiolated substrate in one embodiment of the present invention.

[0020] FIG. 5 is a diagram showing the durability of the anti-fogging film of the present invention measured weekly in one embodiment of the present invention.

[0021] Hereinafter, the present invention will be described in detail with reference to the attached drawings as embodiments of the present invention. However, the following embodiments are presented as examples of the present invention, and if it is determined that a detailed description of a technology or configuration well known to those skilled in the art may unnecessarily obscure the gist of the present invention, the detailed description may be omitted, and the present invention is not limited thereby. The present invention is capable of various modifications and applications within the scope of the following claims and equivalents interpreted therefrom.

[0022] In addition, the terminology used in this specification is a term used to appropriately express preferred embodiments of the present invention, and this may vary depending on the intention of the user or operator, or the customs of the field to which the present invention belongs. Therefore, the definition of these terms should be determined based on the contents throughout this specification. Throughout the specification, when a part is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless specifically stated otherwise.

[0023] Unless otherwise defined, all technical terms used in this invention have the same meaning as commonly understood by those skilled in the art. While preferred methods and materials are described herein, similar or equivalent methods are also included within the scope of the present invention. The contents of all publications cited as references herein are incorporated herein by reference.

[0024] Throughout this specification, '%' used to indicate the concentration of a particular substance is (w / w) % for solid / solid, (w / v) % for solid / liquid, and (v / v) % for liquid / liquid, unless otherwise stated.

[0025] The present invention provides an anti-fogging film comprising an ionic polymer; an allyl polymer; a crosslinking agent; and a photoinitiator.

[0026] In one embodiment, the ionic polymer is at least one selected from the group consisting of trimethyl methacrylate ammonium chloride (TMAC), 3-sulfopropyl methacrylate potassium salt (3-SPMK), sodium acrylate (NaA), sodium methacrylate (NaMA), 2-methacryloyloxyethyl phosphorylcholine (MPC), 2-methacryloyloxyethyl dimethyl-3-sulfopropyl ammonium hydroxide (SBMA), but is not limited thereto, preferably trimethyl methacrylate ammonium It may also be Trimethyl Methacrylate Ammonium Chloride, TMAC).

[0027] In one embodiment, the allyl polymer may be at least one selected from the group consisting of allyl methacrylate (PAMA), norbornene methacrylate (NMA), norbornene acrylate (NA), maleimide acrylate (MA), and maleimide methacrylate (MMA), but is not limited thereto, and preferably may be allyl methacrylate (PAMA).

[0028] In addition, the above-mentioned allyl polymer has the effect of photocrosslinking functionality.

[0029] In one embodiment, the crosslinking agent is tetrakis(3-mercaptopropionate) (PETMP), 1,2-ethanedithiol, 1,4-benzenedimethanethiol, 2,2'-ethylenedioxy diethanethiol, poly(ethylene glycol) dithiol, benzene-1,2-dithiol, benzene-1,4-dithiol, tetra(ethylene glycol) dithiol, biphenyl-4,4'-dithiol, trithiocyanuric acid, It may be at least one member from the group consisting of trimethylolpropane tris(3-mercaptopropionate), tetrakis(3-mercaptopropionate), but preferably tetrakis(3-mercaptopropionate)tetrakis(3-mercaptopropionate)(PETMP).

[0030] In one embodiment, the photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP), 2-benzyl-2-(dimethylamino)-1-(4-(4-morpholinyl) phenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, diaminobenzo phenone, 2-methyl-1-[4-(methylthio)phenyl]-2-Mortholino It may be at least one selected from the group consisting of 2,4-diethyl thioxantone-9-one, 4-(dimethylamino)benzoic acid 3-MB, phenylbis(2,4,6-trimethyl-benzoyl)phosphinoxide, and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, but is not limited thereto, and preferably lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP).

[0031] In one embodiment, the ionic polymer and the allylic polymer may be synthesized by a free radical polymerization method, but is not limited thereto.

[0032] In one embodiment, the crosslinking agent and photoinitiator may be crosslinked by ultraviolet rays, but are not limited thereto.

[0033] The present invention comprises a step of synthesizing an ionic polymer and an allylic polymer using a free radical polymerization method; and

[0034] A method for manufacturing an anti-fogging film is provided, comprising the step of adding a crosslinking agent and a photoinitiator to the synthesized composite and crosslinking with ultraviolet rays.

[0035] The present invention provides a fogging prevention plate having a thiolated substrate; and an anti-fogging film as described above adhered to one side thereof.

[0036]

[0037] In one embodiment, the anti-fogging film may be adhered to only one side of the thiolated substrate, but is not limited thereto, and may be adhered to both sides by adhering to one side and the opposite side.

[0038] In one embodiment, the bonding method may be, but is not limited to, roll-to-roll, dip coating, bar coating, spin coating, or blade coating.

[0039] The above substrate may be, but is not limited to, one or more of the group consisting of glass, metal, oxide and plastic.

[0040] Accordingly, the present invention is characterized in that it uses a method of thiolating OH groups of a substrate using a UV-ozone device, and forms thiol groups on the substrate to improve chemical bonding strength with the composition.

[0041] By measuring the transmittance of the anti-glare film, we can determine how well the film allows light to pass through, ensuring that the surface to which the film is applied remains transparent and provides a clear view.

[0042] The key function of anti-fog film is to prevent water from condensing on the surface, which is measured by how well it absorbs and disperses water. A high water absorbency means that the film disperses water well, helping to reduce light scattering caused by water droplets on the surface.

[0043] The present invention will be described in more detail below through the following manufacturing examples and working examples. However, the following examples are merely illustrative examples intended to easily illustrate the content and scope of the technical concept of the present invention and are not intended to limit or alter the technical scope of the present invention. Furthermore, those skilled in the art will readily determine that various modifications and variations are possible within the scope of the technical concept of the present invention based on these examples.

[0044]

[0045] Manufacturing Example 1. Method for manufacturing an anti-fogging film of the present invention

[0046] Manufacturing Example 1-1. Synthesis

[0047] In order to manufacture the anti-fogging film of the present invention, a copolymer of poly(trimethyl methacrylate) ammonium chloride (PTMAC) and poly(allyl methacrylate) (PAMA) was synthesized as an ionic polymer (or ammonium-based) PTMAC-co-PAMA polymer by a free radical polymerization method (Fig. 1).

[0048] Poly(trimethyl methacrylate)ammonium chloride (PTMAC)) and poly(allyl methacrylate) (PAMA) were synthesized at various ratios (100:1, 100:3, 100:5), and finally, the synthesis was carried out at a ratio of 100:1 (w / w).

[0049]

[0050] Manufacturing Example 1-2. Manufacturing of the anti-fogging film of the present invention

[0051] In order to manufacture the anti-fogging film of the present invention, a crosslinking agent and a photoinitiator were added to the PTMAC-co-PAMA polymer synthesized in Manufacturing Example 1-1, and crosslinking was performed with ultraviolet rays to manufacture the anti-fogging film of the present invention.

[0052] First, the PTMAC-co-PAMA polymer synthesized in Manufacturing Example 1-1, a multi-functional thiol, and an aqueous photoinitiator solution were applied to a substrate (glass, metal, or polymer film), and the film was irradiated with ultraviolet rays having a wavelength of 365 nm and an intensity of 10 to 50 mW / cm2 to manufacture an anti-fogging film.

[0053] The multifunctional thiol used in Manufacturing Example 1-2 was tetrakis(3-mercaptopropionate)(PETMP), and the photoinitiator was lithium phenyl-2,4,6-trimethylbenzo-ylphosphinate (LAP).

[0054]

[0055] Example 1. Confirmation of the anti-fogging effect of the anti-fogging film of the present invention.

[0056] Example 1-1. Measurement of transmittance

[0057] To confirm the anti-fogging effect of the anti-fogging film of the present invention, the transmittance was measured.

[0058] As a result of the measurement, when the anti-fog film of the present invention was not coated on the glass, the transmittance was measured to be approximately 50% when exposed to water vapor. On the other hand, when the anti-fog film of the present invention was applied to the glass, the transmittance was confirmed to be approximately 90% (Fig. 2).

[0059] Therefore, it was confirmed that the anti-fogging film of the present invention has an excellent effect in preventing fogging.

[0060]

[0061] Example 1-2. Absorbance measurement

[0062] In order to confirm the anti-fogging effect of the anti-fogging film of the present invention, the moisture absorption rate and speed were measured.

[0063] As a result of the measurement, after applying the anti-fogging film of the present invention to glass, a water droplet was dropped on the glass, and it was confirmed that the contact angle was 12.8 degrees at 5 seconds, but the contact angle was 9.4 degrees at 10 seconds, indicating that the water droplet was quickly absorbed into the surface (Fig. 3).

[0064]

[0065] Example 2. Bonding strength of the anti-fogging film of the present invention

[0066] In order to introduce a strong chemical bond to the anti-fogging layer of the anti-fogging film of the present invention, the OH group on the surface of a general substrate was substituted with thiol to induce a click reaction with the synthesized polymer.

[0067] The thiolation method was performed using a UV-Ozone or O2 plasma device, and the thiolated substrate was formed through a double bond and click reaction of the synthesized polymer, as shown in Fig. 4.

[0068] The synthesized PTMAC-co-PAMA polymer is readily cross-linked by UV irradiation and forms a chemical bond with a thiolated substrate, making it a suitable technology for implementing high durability. To measure the durability, the anti-fogging performance was measured while exposed to moisture for 6 weeks.

[0069] Therefore, an anti-fogging film with easy processing and strong durability was confirmed through a cross-linked polymer with anti-fogging function and a thiolization process.

[0070]

[0071] The present invention has been described above, focusing on preferred embodiments thereof. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as encompassed by the present invention.

[0072] The present invention develops a polymer capable of photoreacting with thiol while having an anti-fogging effect, thereby developing a polymer film that is durable for a long period of time and exhibits high chemical adhesion to a substrate, and can be usefully used in related businesses.

Claims

1. Ionic polymer; Allyl polymer; crosslinking agent; and Anti-fogging film containing a photoinitiator.

2. In paragraph 1, An anti-fogging film comprising at least one selected from the group consisting of the above ionic polymers: Trimethyl Methacrylate Ammonium Chloride (TMAC), 3-Sulfopropyl Methacrylate Potassium Salt (3-SPMK), Sodium Acrylate (NaA), Sodium Methacrylate (NaMA), 2-Methacryloyloxyethyl Phosphorylcholine (MPC), and 2-Methacryloyloxyethyl Dimethyl-3-Sulfopropyl Ammonium Hydroxide (SBMA).

3. In paragraph 1, An anti-fogging film comprising at least one selected from the group consisting of allyl methacrylate (PAMA), nobornene methacrylate (NMA), nobornene acrylate (NA), maleimide acrylate (MA), and maleimide methacrylate (MMA).

4. In paragraph 1, The crosslinking agent is tetrakis(3-mercaptopropionate)(PETMP), 1,2-ethanedithiol, 1,4-benzenedimethanethiol, 2,2'-ethylenedioxy diethanethiol, poly(ethylene glycol) dithiol, benzene-1,2-dithiol, benzene-1,4-dithiol, tetra(ethylene glycol) dithiol, biphenyl-4,4'-dithiol, trithiocyanuric acid, triethylene glycolpropane. An anti-fogging film comprising at least one selected from the group consisting of tris(3-mercaptopropionate) (Trimethylolpropane tris(3-mercaptopropionate)), tetrakis(3-mercaptopropionate) (tetrakis(3-mercaptopropionate)).

5. In paragraph 1, The photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP), 2-benzyl-2-(dimethylamino)-1-(4-(4-morpholinyl) phenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, diaminobenzo phenone, 2-methyl-1-[4-(methylthio)phenyl]-2-Mortholino An anti-fogging film comprising at least one selected from the group consisting of 2,4-diethyl thioxantone-9-one, 4-(dimethylamino)benzoic acid 3-MB, phenylbis(2,4,6-trimethyl-benzoyl)phosphinoxide, and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

6. In paragraph 1, An anti-fogging film comprising the above ionic polymer and an allylic polymer synthesized by a free radical polymerization method.

7. In paragraph 1, An anti-fogging film comprising the above crosslinking agent and photoinitiator crosslinked by ultraviolet rays.

8. A step of synthesizing an ionic polymer and an allylic polymer using a free radical polymerization method; and A method for manufacturing an anti-fogging film, comprising the step of adding a crosslinking agent and a photoinitiator to the synthesized composite and crosslinking with ultraviolet rays.

9. A thiolated substrate; an anti-fogging plate having the anti-fogging film of claim 1 attached to one side thereof.

10. In paragraph 9, The above bonding method includes bonding by roll-to-roll, dip coating, bar coating, spin coating, and blade coating.

11. In paragraph 9, The above substrate is a fogging prevention plate comprising at least one member selected from the group consisting of glass, metal, oxide and plastic.

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