KR102613426B1 - Surface protection film for anti static and infrared reflection - Google Patents

Abstract

The present invention relates to a surface protection film for antistatic and infrared blocking purposes. The present invention relates to a base film; and a coating layer located on one side of the base film, wherein the coating layer includes graphene quantum dots and vanadium dioxide.

Description

Surface protection film for anti-static and infrared blocking {SURFACE PROTECTION FILM FOR ANTI STATIC AND INFRARED REFLECTION}

The present invention relates to a surface protection film for antistatic and infrared blocking purposes.

Electricity remaining on an object containing metal elements is called static electricity. When another object touches an object with static electricity, a voltage of more than 10,000 volts is instantly generated. Because electricity flows for a very short time, injuries from static electricity are rare. However, because it has an instantaneous ignition effect, an explosion or fire accident may occur due to static electricity in oil or flammable substances.

Additionally, if you touch an object with static electricity, the electricity will instantly flow and you will feel a stinging and unpleasant sensation. Especially in winter, when a lot of static electricity is generated, people become reluctant to touch metal handles, metal chairs, etc. left outside.

Meanwhile, in the summer when the temperature rises, due to the nature of metal with high thermal conductivity, the metal heats up to a very high temperature, making it difficult to touch metal handles, metal chairs, etc. left outside with your hands.

Korean Patent Publication No. 10-2016-0056533

Korean Patent Publication No. 10-2017-0004940

The present invention recognizes the above problems and aims to provide an antistatic and infrared blocking surface protection film that prevents temperature rise and does not generate static electricity.

Another object of the present invention is to provide an antistatic and infrared blocking surface protection film that prevents temperature rise, does not generate static electricity, and can be used for a long period of time.

The objects of the present disclosure are not limited to the purposes mentioned above, and other objects and advantages of the present disclosure that are not mentioned can be understood by the following description and will be more clearly understood by the examples of the present disclosure. Additionally, it will be readily apparent that the objects and advantages of the present disclosure can be realized by the means and combinations thereof indicated in the patent claims.

The present invention relates to a base film; and a coating layer located on one side of the base film, wherein the coating layer includes graphene quantum dots and vanadium dioxide.

The base film may be one or more polymer films selected from polyethylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyetherimide, polyamidoimide, polyimide, and polybenzoxazole.

The graphene quantum dot may have vanadium dioxide bonded to the surface.

The coating layer may further include graphene quantum dots with vanadium dioxide and PEDOT bonded to the surface.

The coating layer contains 50 to 80 parts by weight of graphene quantum dots with a sphericity of 0.7 or more with vanadium dioxide and PEDOT bonded to the surface for 100 parts by weight of graphene quantum dots with a sphericity of 0.9 or more with vanadium dioxide and PEDOT bonded to the surface. You can.

The coating layer may further include one or more of epoxy resin, silicone resin, photocurable resin, ethylcellulose, and polyvinyl butyral.

The present invention also includes the steps of preparing a base film; and forming a coating layer on one side of the base film, wherein the coating layer includes graphene quantum dots and vanadium dioxide.

The step of forming the coating layer includes graphene quantum dots with a sphericity of 0.9 or more in which vanadium dioxide is bonded to the surface, graphene quantum dots with a sphericity of 0.7 or more in which vanadium dioxide and PEDOT are bonded to the surface, polyvinyl butyral, and ethanol. It may be a step of forming by mixing.

According to the present invention, it is possible to provide an antistatic and infrared blocking surface protection film that prevents temperature rise and does not generate static electricity.

The surface protection film for antistatic and infrared blocking of the present invention has an infrared blocking or reflecting effect when the temperature rises, preventing the temperature of the object to which the protective film is attached from rising excessively in the summer, and absorbing light to prevent the object to which the protective film is attached in the winter. It can prevent the temperature from dropping excessively.

1 is a cross-sectional view of a surface protection film for antistatic and infrared blocking according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing the mechanism by which vanadium dioxide binds to the surface of graphene quantum dots.

Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, suitable methods and materials are described herein.

When referred to herein as a component being disposed “on” or “on” another component, the component may be disposed directly on the other component or may have components intervening between the components. It could exist. On the other hand, when an element is referred to as being disposed “directly on” or “directly on” another element, intervening elements may not be present.

1 is a cross-sectional view of a surface protection film for antistatic and infrared blocking according to an embodiment of the present invention.

Referring to FIG. 1, the antistatic and infrared blocking surface protection film 100 according to one embodiment of the present invention has a structure in which a base film 110 and a coating layer 120 are stacked in that order. The thickness of the surface protection film 100 is 3 mm or less, and if it is more than 3 mm, it is difficult to attach the protection film to the surface of the object.

Base film (110)

The base film 110 may be, for example, a transparent film. The base film 110 has both light transparency and thermal stability. The base film 110 may be a transparent flexible polymer film. For example, the base film 110 may be one or more polymer films selected from polyethylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyetherimide, polyamidoimide, polyimide, and polybenzoxazole. You can.

For example, the base film 110 may be polyethylene terephthalate. However, it is not limited thereto, and the polymer film may further include other polymers having sufficient optical properties such as sufficient mechanical/thermal stability for specific applications and high transmittance of light with a specific wavelength.

The base film 110 according to one embodiment may have a single layer or a multi-layer structure of two or more layers. When the base film 110 has a multilayer structure of two or more layers, the polymer materials constituting each layer may all be the same or different from each other.

The thickness of the base film 110 may be 0.1 to 3 mm.

The polymer used in the base film 110 is primer-treated or roughened to improve adhesion to the surface of an object or the coating layer 120, or stretched, heat-treated, or water-repellent treated to improve thermal stability. Alternatively, it may contain a small amount of fine particles or fillers to control light permeability, or may be water-repellent treated.

Coating layer (120)

The coating layer 120 may have a thickness of 0.00001 mm to 1 mm.

The composition for forming a coating layer on the base film 110 is sprayed, brush coated, curtain-flow coated, gravure coated, roll coated, spin coated, or bar coated. It can be prepared by applying using known coating methods such as (bar) coating and electrostatic coating. Drying temperature can be appropriately selected depending on the solvent.

The coating layer 120 may include graphene quantum dots and vanadium dioxide. The coating layer 120 may additionally include poly(3,4-ethylenedioxythiophene) (PEDOT). Vanadium dioxide is bonded to the surface of the graphene quantum dot. Additionally, PEDOT and vanadium dioxide may be bonded to the surface of the graphene quantum dot.

The coating layer 120 may include polymer resin for forming a coating layer. For example, it may include thermosetting resins such as epoxy resin and silicone resin, photocurable resin such as UV curable resin may be used, and ethylcellulose and polyvinyl butyral may be used. there is. The solvent used to form the coating layer may be chloroform, ethanol, or propylene glycol monomethyl ether.

In particular, when ethanol as a solvent and polyvinyl butyral as a polymer resin are used, the adhesion of the coating layer to the base film is excellent, and the hardness and strength of the coating layer are excellent. More specifically, when polyvinyl butyral and graphene quantum dot particles are included in an amount of 0.1 to 30 wt% based on 100 wt% of ethanol, adhesion to the base film is excellent, and the hardness and strength of the coating layer are excellent.

The coating layer 120 is composed of 50 to 80 parts by weight of graphene quantum dots with a sphericity of 0.7 or more with vanadium dioxide and PEDOT bonded to the surface for 100 parts by weight of graphene quantum dots with a sphericity of 0.9 or more with vanadium dioxide and PEDOT bonded to the surface. It may include When included in the above mixing ratio, the durability and long-term usability of the coating layer are excellent.

The graphene quantum dot refers to nano-sized graphene fragments. Each graphene quantum dot may have a multi-layer structure. For example, graphene quantum dots may have a multi-layer structure of approximately 10 layers or less, but are not limited to this. Graphene quantum dots can be formed through, for example, electron beam lithography, chemical synthesis, hydrothermal method, etc.

In this implementation, each graphene quantum dot may have a nano-sized spherical shape. For example, graphene quantum dots may have a diameter of approximately 10 nm to 60 nm. As a more specific example, graphene quantum dots may have a diameter of approximately 3 nm to 4 nm. However, this is just an example, and graphene quantum dots may have various other diameters.

The vanadium dioxide (VO ₂ ) is a metal-insulator phase transition material and has the characteristic of a metal-insulator phase transition that occurs at a speed of several tens of femtoseconds (10-15 units, i.e., 1 trillionth of a second) at about 66°C. The vanadium dioxide is a metal oxide, and when mixed with graphene quantum dots, it combines with functional groups present on the surface of the graphene quantum dots. More specifically, as shown in Figure 2, carboxylic acid and metal cations present on the surface of graphene quantum dots combine through an acid-base reaction.

Graphene quantum dots with vanadium dioxide bonded on the surface have anti-static and infrared blocking effects in the coating layer.

PEDOT is a conductive polymer. PEDOT is combined with vanadium dioxide on the surface of graphene quantum dots. The PEDOT improves the anti-static effect when mixed with graphene quantum dots.

^The surface resistance of the coating layer ^{120 is} preferably 1.0 There is an antistatic effect within the above surface resistance value range, and dust does not bind to the surface.

The higher the sphericity of graphene quantum dots with vanadium dioxide bonded to the surface, the better the effect of reflecting or blocking infrared rays at high temperatures. However, when only graphene quantum dots with high sphericity are used, the reflectance or blocking rate is drastically reduced due to contamination from rainwater and dust when used outdoors for a long period of time. The sphericity refers to the ratio calculated by the projected area and peripheral length of the particle measured with a scanning electron microscope.

In the present invention, in order to solve this problem, PEDOT with low sphericity and graphene quantum dots with vanadium dioxide bonded to the surface are used together to prevent contamination from rainwater and dust during long-term use, thereby improving the durability and long-term use of the protective film. Improves usability.

In one embodiment of the present invention, the method for producing graphene quantum dots having vanadium dioxide and PEDOT formed on the surface is as follows: mixing vanadium dioxide and graphene quantum dot particles to produce vanadium dioxide-graphene quantum dot particles. manufacturing step; A step of mixing EDOT (3,4-ethylenedioxythiophene) and vanadium dioxide-graphene quantum dot particles and performing an electrochemical oxidation reaction.

The anti-static and infrared blocking surface protection film 100 according to an embodiment of the present invention is attached to the surface of an object such as a chair or handle, preventing overheating by solar heat in the summer and preventing the accumulation of static electricity in the winter. You can.

The configuration of the present invention and its effects will be described in more detail through examples and comparative examples below. However, these examples are for specifically illustrating the present invention, and the scope of the present invention is not limited to these examples.

Example

Preparation Example 1: Vanadium dioxide-graphene quantum dot (VO ₂ -GQD) preparation

Carbon nanofibers (3.0 g) were added to a mixed solution of concentrated H ₂ SO ₄ (72 mL) and HNO ₃ (24 mL), sonicated for 1 hour, and stirred at 110°C for 1 day to form graphene quantum. manufactures dots. After cooling, the VO ₂ precursor saturated solution is mixed. The VO ₂ -GQDs are then separated through selective precipitation by centrifugation several times at 12,000 rpm for 30 minutes. Ethanol is added to the reaction solution at a volume ratio of 1:1 to precipitate impurities and large GQDs. The precipitate and supernatant were separated by centrifugation at 12,000 rpm for 30 minutes. Ethanol was added again at 1:1 v/v% to the supernatant obtained after the first centrifugation, and the solution was centrifuged at 12,000 rpm for 30 minutes. This process is repeated several times to obtain VO ₂ -GQDs of uniform size and remove impurities. The sphericity of the formed VO ₂ -GQDs was 0.93.

Preparation Example 2: PEDOT/vanadium dioxide-graphene quantum dot (PEDOT/VO ₂ -GQD) preparation

PEDOT/VO ₂ -GQDs are prepared by electrochemical method. Specifically, it was fabricated via electropolymerization of EDOT on graphene carbon electrodes using cyclic voltammetry (CV) with an applied potential range of 0.5–1.7 V for 30 cycles at a scan rate of 100 mV s ^-1 . The electrochemical cell for forming the PEDOT/VO ₂ -GQD film was H ₂ O:CH ₃ CN (1:9 v/v) containing 0.01M EDOT as a monomer and 1.0 wt% VO ₂ -GQD as a supporting electrolyte and dopant. The mixture was prepared using three electrodes (reference electrode (Ag/Ag(NO) ₃ ; working electrode (graphene carbon electrode), counter electrode (Pt))). The surface of the electropolymerized PEDOT thin film was coated with CH ₃ CN. Unreacted monomers were removed by careful washing several times. Afterwards, the PEDOT/VO ₂ -GQD film attached to the electrode surface was scraped from the electrode and stored in a glass container. The sphericity of the PEDOT/VO ₂ -GQD thus formed was It was 0.7.

Example 1

Prepare a polyethylene terephthalate (PET) film with a thickness of 0.1 mm as a base film. A composition for forming a coating layer was prepared by mixing 150 parts by weight of VO ₂ -GQD of Preparation Example 1 with 100 parts by weight of polyvinyl butyral and 1,000 parts by weight of ethanol solvent.

The composition was applied to one side of the base film and dried to form a coating layer.

Example 2

Prepare a polyethylene terephthalate (PET) film with a thickness of 0.1 mm as a base film. A composition for forming a coating layer was prepared by mixing 150 parts by weight of PEDOT/VO ₂ -GQD of Preparation Example 2 with 100 parts by weight of polyvinyl butyral and 1,000 parts by weight of ethanol solvent.

The composition was applied to one side of the base film and dried to form a coating layer.

Example 3

Prepare a polyethylene terephthalate (PET) film with a thickness of 0.1 mm as a base film. A composition for forming a coating layer was prepared by mixing 100 parts by weight of VO ₂ -GQD of Preparation Example 1, 50 parts by weight of PEDOT/VO ₂ -GQD of Preparation Example 2, 100 parts by weight of polyvinyl butyral, and 1000 parts by weight of ethanol solvent.

The composition was applied to one side of the base film and dried to form a coating layer.

Example 4

In Example 3, except that 110 parts by weight of VO ₂ -GQD of Preparation Example 1, 40 parts by weight of PEDOT/VO ₂ -GQD of Preparation Example 2, 100 parts by weight of polyvinyl butyral, and 1000 parts by weight of ethanol solvent were used, A surface protective film was prepared in the same manner as in Example 3.

Example 5

In Example 3, except that 75 parts by weight of VO ₂ -GQD of Preparation Example 1, 75 parts by weight of PEDOT/VO ₂ -GQD of Preparation Example 2, 100 parts by weight of polyvinyl butyral, and 1000 parts by weight of ethanol solvent were used, A surface protective film was prepared in the same manner as in Example 3.

Example 6

In Example 3, a composition for forming a coating layer was prepared by mixing 100 parts by weight of VO ₂ -GQD of Preparation Example 1, 50 parts by weight of PEDOT/VO ₂ -GQD of Preparation Example 2, 100 parts by weight of ethylcellulose, and 1000 parts by weight of chloroform solvent. Manufactured.

Comparative Example 1

In Example 1, a surface protection film was prepared in the same manner as Example 1, except that GQD was used instead of VO ₂ -GQD in Preparation Example 1.

Comparative Example 2

In Example 1, a surface protection film was manufactured in the same manner as Example 1, except that VO ₂ was used instead of VO ₂ -GQD in Preparation Example 1.

Experimental Example 1

Antistatic properties and infrared transmittance were measured for the surface protection films prepared in the above examples and comparative examples. Antistatic properties were measured using an antistatic measuring instrument (Mitsubishi Co., Ltd.; model name MCP-T600), after leaving the sample in an environment of temperature 23°C and humidity 10, 50, and 80%RH for 1 hour, and then measuring surface resistance in accordance with JIS K7194. . Infrared transmittance was measured at 25°C and 60°C for wavelengths of 700 to 800 nm using a spectrophotometer. The results are shown in the table below.

Surface resistance (Ω/□) 25℃ infrared transmittance (%) 60℃ infrared transmittance (%) Example 1 5 x 10 ⁸ 44 30 Example 2 4 x 10 ⁷ 32 29 Example 3 8 x 10 ⁷ 38 33 Example 4 2 x 10 ⁸ 40 30 Example 5 7 x 10 ⁷ 35 31 Example 6 6 x 10 ⁷ 39 32 Comparative Example 1 5 x 10 ¹⁰ 63 65 Comparative Example 2 3 x 10 ¹² 40 25

As shown in the table above, the surface protection film of the example had an excellent antistatic effect and an infrared blocking effect at high temperatures compared to the surface protection film of the comparative example.

Experimental Example 2

After the surface protection film prepared in the above Examples and Comparative Examples was left outdoors for 3 months, the surface resistance and transmittance were measured in the same manner as in Experimental Example 1, and the rate of change (%) was calculated by comparing with Table 1.

Surface resistance change rate (%) Rate of change in infrared transmittance at 25℃ (%) Rate of change in infrared transmittance at 60℃ (%) Example 1 13 12 10 Example 2 15 13 11 Example 3 5 4 3 Example 4 8 7 8 Example 5 10 9 9 Example 6 6 5 5 Comparative Example 1 16 15 12 Comparative Example 2 14 13 12

As shown in the table above, it was confirmed that the surface protection film containing both VO ₂ -GQD and PEDOT/VO ₂ -GQD had a small change in surface resistance and transmittance even after being left for a long time, and could be used for a long time. In particular, the surface protection film of Example 3 containing 50 parts by weight of PEDOT/VO ₂ -GQD relative to 100 parts by weight of VO ₂ -GQD had the best long-term usability.

Experimental Example 3

The surface protection film prepared in the above examples and comparative examples was attached to a metal iron bar, left outdoors for 3 hours in sunlight at 30°C or higher, or left outdoors at 0 to 5°C for 3 hours, and then the surface temperature was measured. The results are shown in the table below.

Outdoor above 30℃ 0~5℃ outdoor Example 1 38℃ 12℃ Example 2 43℃ 14℃ Example 3 41℃ 13℃ Example 4 40℃ 12℃ Example 5 44℃ 13℃ Example 6 42℃ 12℃ Comparative Example 1 53℃ 9℃ Comparative Example 2 39℃ 10℃

As shown in the table above, it was confirmed that the surface protection film of the example had a small temperature rise in a high temperature environment and a small temperature drop in a low temperature environment. Experimental Example 4

The adhesion and hardness of the surface protective films prepared in the above examples and comparative examples were measured.

The adhesion evaluation method is as follows: Attach a surface protection film to a metal object, cut it into 1mm x 1mm units to prepare 100 samples, then attach the tape and tear it off. The number of samples remaining on the object surface was evaluated.

The hardness evaluation method was as follows: Pencils of various hardnesses were prepared, the pencil was placed on the surface protection film and scratched with a certain weight to measure the degree of damage to the surface.

Adhesion Hardness Example 1 82/100 3H Example 2 75/100 3H Example 3 77/100 3H Example 4 83/100 3H Example 5 80/100 3H Example 6 61/100 2H Comparative Example 1 72/100 3H Comparative Example 2 75/100 3H

As shown in the table above, it was confirmed that the hardness and adhesion of the produced film were excellent when polyvinyl butyral as the polymer resin and ethanol as the solvent were used.

Claims (8)

base film; and
It includes a coating layer located on one side of the base film,
The coating layer includes graphene quantum dots and vanadium dioxide,
The graphene quantum dot has vanadium dioxide bonded to the surface.
The coating layer further includes graphene quantum dots with vanadium dioxide and PEDOT bonded to the surface,
The coating layer includes 50 to 80 parts by weight of graphene quantum dots with a sphericity of 0.7 or more with vanadium dioxide and PEDOT bonded to the surface for 100 parts by weight of graphene quantum dots with a sphericity of 0.9 or more with vanadium dioxide and PEDOT bonded to the surface. Surface protection film for phosphorus, anti-static and infrared blocking According to paragraph 1,
The base film is an antistatic and infrared blocking film made of at least one polymer film selected from polyethylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyetherimide, polyamideimide, polyimide, and polybenzoxazole. Surface protection film. delete delete delete According to paragraph 1,
The coating layer is an antistatic and infrared blocking surface protection film that further includes one or more of epoxy resin, silicone resin, photocurable resin, ethylcellulose, and polyvinyl butyral. . Preparing a base film; and
It includes forming a coating layer on one side of the base film,
The step of forming the coating layer includes graphene quantum dots with a sphericity of 0.9 or more in which vanadium dioxide is bonded to the surface, graphene quantum dots with a sphericity of 0.7 or more in which vanadium dioxide and PEDOT are bonded to the surface, polyvinyl butyral, and ethanol. This is the step of forming by mixing,
A method of manufacturing a surface protection film for antistatic and infrared blocking, wherein the coating layer includes graphene quantum dots and vanadium dioxide. delete