KR20240100688A - Method for manufacturing low-reflection coating material and low-reflection coating composition - Google Patents

Abstract

The present invention is a method of manufacturing a low-reflection coating material, and more specifically, mixing a first material containing an acrylate and a second material containing a multifunctional acrylate to synthesize a third material that is a low refractive index material. , During the synthesis process, the third material is reacted for a sufficient period of time to turn it into a macromolecule, and then the third material, which has become a gel due to the macromolecularization, is liquefied through ultrasonic treatment, and then the third material, the high refractive material, and the binder are mixed. It relates to a method of manufacturing a single-layer low-reflection coating material.

Description

Method for manufacturing anti-reflection coating material and anti-reflection coating composition}

The present invention relates to a method for manufacturing a low-reflection coating material and a low-reflection coating composition, and more specifically, to produce a low-refractive material by mixing a first material containing an acrylate and a second material containing a multifunctional acrylate. After synthesizing the three materials and reacting them for sufficient time during the synthesis process to turn the third material into macromolecules, the third material, which has become a gel due to macromoleculeization, is liquefied through ultrasonic treatment, and then the third material and the high refractive material are liquefied. , relates to a method of manufacturing a single-layer low-reflection coating material by mixing a binder, and a low-reflection coating composition.

Various forms of displays are now common but important entities that can be seen everywhere in our daily lives. Among these, displays for vehicles, mobile devices, TVs, monitors, exhibition windows, etc. are provided with a low-reflection coating to improve the quality of the display in order to provide a high-quality screen or because the display is difficult to see due to ambient light due to the nature of being used outdoors. I order it.

This low-reflection coating is typically implemented by forming multiple layers of thin films with different refractive indices. A variety of polymer films for low-reflection coatings already exist throughout the industry. The physical principles of these low-reflection coatings are already widely known, and to put it briefly, low-reflection coatings are composed of polymer layers of a high-refractive-index material and a low-refractive-index material. In other words, it consists of a laminated structure in which these polymer layers are stacked.

Therefore, the low-reflection coating is made of a multi-layer thin film made by stacking several thin films with different refractive indices, such as a high refractive index thin film and a low refractive index thin film, in multiple layers.

Multilayer thin films of general low-reflection coatings are formed using methods such as vacuum deposition.

The preferred thickness of the multilayer thin film is about 1/4 of the wavelength to be reflected. In other words, a thickness of 1/4 of the visible light range of 300 to 700 nm is desirable, and multilayer thin films formed by vacuum deposition generally have a thickness of 100 nm or less.

Therefore, the strength of these multilayer thin films is weak and has serious disadvantages in durability, such as weak environmental resistance, weak abrasion resistance, and being easily damaged by friction.

These shortcomings are especially noticeable when low-reflection coatings are applied to fields where wear resistance is important, such as automotive displays. The outermost coating of a vehicle display requires characteristics such as low reflection, high hardness, anti-pollution, anti-finger, and anti-scratch. It is difficult for multi-layer thin-film low-reflection coatings made by vacuum deposition to satisfy all of these functions, and because they require multi-step processes in high vacuum, they have low efficiency in terms of economic feasibility and business performance.

Therefore, the need for a single-layer coating material to solve the shortcomings of the existing multilayer thin film for low-reflection coating is becoming prominent.

Meanwhile, Korean Patent No. 10-1548313 relates to a composition for low-reflection coating that can exhibit excellent scratch resistance, and more specifically, a photopolymerizable compound, hollow silica particles, polyethersiloxane-based polymer, and photopolymerization initiator. It relates to an anti-reflection film comprising a low-reflection coating composition comprising a low-reflection coating layer and a low-reflection coating layer formed from the composition. The composition for low-reflection coating according to the present invention describes a method of providing a low-reflection coating layer with excellent surface scratch resistance without reducing the clarity of the screen due to low light reflectance and high light transmittance.

However, since the prior patent is also a technology for forming a thin film with a multi-layer structure, it has limitations in thin films with a multi-layer structure.

Considering this, the present invention provides a method of manufacturing a single-layer low-reflection coating thin film using a mixture of a low refractive index material and a high refractive index material.

Korean Patent No. 10-1548313

The present invention is a method of manufacturing a low-reflection coating material, and more specifically, mixing a first material containing an acrylate and a second material containing a multifunctional acrylate to synthesize a third material that is a low refractive material. , During the synthesis process, the third material is reacted for a sufficient period of time to turn it into a macromolecule, and then the third material, which has become a gel due to the macromolecularization, is liquefied through ultrasonic treatment, and then the third material, the high refractive material, and the binder are mixed. It relates to a method of manufacturing a single-layer low-reflection coating material.

In order to solve the above problems, the present invention includes a mixing step of mixing a first material containing an acrylate and a second material containing a multifunctional acrylate; A heating step of heating the mixed first and second materials; An ultrasonic treatment step of sonicating a third material formed by heating the first material and the second material;　And a coating material manufacturing step of mixing a third material on which ultrasonic treatment was performed, a high refractive index material having a higher refractive index than the third material, and a UV-curable urethane binder, followed by stirring to produce a coating material. A method of manufacturing a reflective coating material is provided.

In some embodiments of the present invention, the heating step includes a first step of adding an initiator that induces a radical chain reaction in a mixture of the first material and the second material; and a second step of heating the first material, the second material, and the starting material at a temperature of 50 to 100°C.

In some embodiments of the present invention, in the heating step, the first material and the second material continuously react by heat, so that the third material formed by the reaction becomes macromolecule and takes the form of a gel, In the ultrasonic treatment step, the third material is converted from a gel form to a liquid form to form a coating layer.

In some embodiments of the present invention, the first material includes fluorinated acrylate, the second material includes multi-functional urethane acrylate, and in the heating step, Heating is performed with the addition of a radical initiator that induces a radical chain reaction, so that a portion of the acrylate site of the polyfunctional urethane acrylate reacts with the acrylate site of the fluorinated acrylate. , another part of the acrylate site of the multifunctional urethane acrylate may not participate in polymerization with the fluorinated acrylate.

In one embodiment of the present invention, the third material after the heating step is performed is a multi-tube formed by reacting a portion of the acrylate site of the multifunctional urethane acrylate with an acrylate site of the fluorinated acrylate. Functional urethane acrylate oligomer; And it may include the fluorinated acrylate that does not participate in the reaction.

In one embodiment of the present invention, the coating layer formed by UV curing of the coating material is dispersed entirely in a UV-curable urethane binder, and the third material is located on the upper side due to a difference in surface tension, and the high refractive index The substance may be located on the lower side.

In one embodiment of the present invention, the coating layer formed by UV curing of the coating material has an overall refractive index gradient formed by the concentration gradient generated according to the difference in surface tension between the third material, which is a low refractive material, and the high refractive material. Provides a method of manufacturing a low-reflection coating material.

According to one embodiment of the present invention, the effect of implementing a single-layer low-reflection coating can be achieved by using a concentration gradient using the difference in surface tension between the low-refractive index material and the high-refractive material.

According to one embodiment of the present invention, by forming the low-reflective coating layer as a single layer, the hardness of the low-reflective coating layer can be improved and anti-fingerprint and scratch resistance can be improved.

According to one embodiment of the present invention, the hardness of the coating layer can be improved by forming a coating layer by UV curing a low-reflection coating material containing a UV binder.

According to one embodiment of the present invention, the third material is synthesized under a reaction time sufficient to gel, thereby converting the third material into macromolecules to improve the refractive index of the coating layer, and the low-reflection coating material containing the third material is conventionally prepared. It can be effective in implementing a low-reflection coating layer that exhibits an excellent low-reflection effect compared to the low-reflection coating layer of .

According to one embodiment of the present invention, by ultrasonicating the gelled third material to liquefy it, the low-reflection coating material can be applied as a low refractive index material that can be formed into a thin film.

Figure 1 schematically shows the manufacturing steps of a low-reflection coating material according to an embodiment of the present invention.
Figure 2 schematically shows a first material, a second material, and a third material according to an embodiment of the present invention.
Figure 3 schematically shows a high refractive index material and a UV-curable urethane binder according to an embodiment of the present invention.
Figure 4 schematically shows a cross section of a low-reflection coating according to an embodiment of the present invention.
Figure 5 is a graph measuring the reflectance in the visible light range of 350 to 750 nm for Examples 1, 2, 3, 4, and 5, and PMMA films without the low-reflection coating layer 600. It is compared and expressed as .

Various embodiments and/or aspects are now disclosed with reference to the drawings. In the following description, for purposes of explanation, numerous specific details are set forth to facilitate a general understanding of one or more aspects. However, it will also be appreciated by those skilled in the art that this aspect(s) may be practiced without these specific details. The following description and accompanying drawings set forth in detail certain example aspects of one or more aspects. However, these aspects are illustrative and some of the various methods in the principles of the various aspects may be utilized, and the written description is intended to encompass all such aspects and their equivalents.

As used herein, “embodiments,” “examples,” “aspects,” “examples,” etc. may not be construed to mean that any aspect or design described is better or advantageous over other aspects or designs. .

Additionally, the term “or” is intended to mean an inclusive “or” and not an exclusive “or.” That is, unless otherwise specified or clear from context, “X utilizes A or B” is intended to mean one of the natural implicit substitutions. That is, either X uses A; X uses B; Or, if X uses both A and B, “X uses A or B” can apply to either of these cases. Additionally, the term “and/or” as used herein should be understood to refer to and include all possible combinations of one or more of the related listed items.

Additionally, the terms "comprise" and/or "comprising" mean that the feature and/or element is present, but exclude the presence or addition of one or more other features, elements and/or groups thereof. It should be understood as not doing so.

Additionally, it will be understood that singular expressions such as “unless” and “the” include plural expressions in this specification, unless otherwise clearly indicated. Thus, in one example, a “component surface” includes one or more component surfaces.

Additionally, terms including ordinal numbers, such as first, second, etc., may be used to describe various components, but the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, a first component may be named a second component, and similarly, the second component may also be named a first component without departing from the scope of the present invention. The term and/or includes any of a plurality of related stated items or a combination of a plurality of related stated items.

Additionally, the terms used in this specification are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

In addition, in the embodiments of the present invention, unless otherwise defined, all terms used herein, including technical or scientific terms, are generally understood by those skilled in the art to which the present invention pertains. It has the same meaning as Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless clearly defined in the embodiments of the present invention, have an ideal or excessively formal meaning. It is not interpreted as

In today's era, displays have become an essential product that can be found anywhere in our daily lives. These displays generally use LCD and OLED, and both displays are manufactured by stacking multiple nanometer to micrometer thin films.

On the outermost layer of these displays, various thin films are laminated to not only emit light but also improve quality, a representative example of which is low-reflection coating.

Low-reflection means a reflectance value that is lower than the reflectance value of a display without any treatment, and low-reflection coating is a thin film formed on the surface of the display that has a reflectance lower than that of a display without any treatment. This refers to the coating layer formed to be measured.

For displays used in places with bright external light such as the sun, such as mobile displays, vehicle displays, and exhibition windows, the external light is reflected from the surface of the display and enters the user's field of view along with the light emitted from the display, allowing the user to properly view the contents of the display. Problems that are difficult to recognize may arise.

To prevent these problems, displays used outdoors or in brightly lit places, such as mobile displays, vehicle displays, and exhibition windows, are treated with a low-reflection coating to minimize external light reflected from the display surface.

The principle of low-reflection coating technology is to cause reflected light to cause destructive interference with each other. The condition for causing interference is that the path difference between the two reflected lights is half the light wavelength, so that the phase difference of the light is 180°. In order to satisfy these interference conditions, the thickness and refractive index value of the anti-reflective coating must be adjusted.

The most widely used low-reflection coating technology is the use of thin films with different refractive indices. By stacking a thin film with a high refractive index and a thin film with a low refractive index on the outermost layer of the display, light is refracted in the thin films with different refractive indexes, causing destructive interference, thereby realizing low reflection.

However, this conventional low-reflection coating technology is formed by stacking several layers of thin films using a method such as vacuum deposition, and the multilayer thin film formed by vacuum deposition has the characteristic of typically having a thickness of 100 nm or less. Therefore, the strength of the multilayer thin film formed by conventional technology is bound to be weak and has limitations such as poor environmental resistance and damage to the thin film due to friction.

These limitations become more apparent when low-reflection coatings are applied to fields such as automotive displays. The outermost coating of a vehicle display requires functions such as low reflection, high hardness, anti-pollution, anti-finger, and anti-scratch.

However, low-reflection coating by vacuum deposition is difficult to satisfy all of these functions and requires a multi-step process in high vacuum, so it is not good from an economic and business perspective.

To solve these various problems, it is necessary to develop a material that can implement a single-layer low-reflection coating with sufficient strength and hardness.

The present invention proposes a method of manufacturing a low-reflection coating material for such a single-layer low-reflection coating.

The low-reflection coating material according to an embodiment of the present invention is formed as a single-layer thin film. Preferably, when fluorinated acrylate oligomer and UV curable binder are mixed inside the micro-meter scale thin film, the fluorinated acrylate and curable acrylate are formed when thermal energy is received. A low-reflection coating is formed as a single-layer thin film by taking advantage of the phenomenon in which fluorinated acrylate moves toward the air layer due to a difference in surface tension and generates a concentration gradient.

In the present invention, in the process of synthesizing the low-reflection coating material, the low-reflection characteristics can be controlled by adjusting the heating time of the mixture used as the material.

Figure 1 schematically shows the manufacturing steps of a low-reflection coating material according to an embodiment of the present invention.

A method of manufacturing the low-reflection coating material according to an embodiment of the present invention includes a first material 100 containing an acrylate, and a first material 100 containing a multifunctional acrylate. A mixing step (S100) of mixing two substances (200); A heating step (S200) of heating the mixed first material 100 and the second material 200; An ultrasonic treatment step (S300) of sonicating the third material 300 formed by heating the first material 100 and the second material 200;　and the first material 100 and the second material 200 on which ultrasonic treatment was performed, the third material 300 on which ultrasonic treatment was performed, and a high refractive index material having a higher refractive index than the third material 300 ( 400) and a coating material manufacturing step (S400) of mixing the UV-curable urethane binder 500 and then performing stirring.

In the mixing step (S100), the first material 100 and the second material 200 are mixed.

The first material 100 includes fluorinated acrylate, preferably 1H,1H,5H-Octafluoropentyl Methacrylate, 1H,1H,2H,2H-Tridecafluoro-n-octyl Acrylate, Fluorinated hexa- It includes one or more of functional urethane acrylate oligomer, and fluorinated di-functional urethane acrylate oligomer.

Additionally, the second material 200 may preferably be multi-functional urethane acrylate.

In the mixing step (S100) according to an embodiment of the present invention, the fluorinated acrylate and the multi-functional urethane acrylate may be placed in one reactor and stirred.

Meanwhile, in one embodiment of the present invention, the reactor may be a beaker and a hot plate.

At this time, the low-reflection coating material may exhibit various physical properties depending on the ratio of the fluorinated acrylate and the multi-functional urethane acrylate, and a more detailed description of this will be provided later. do.

The heating step (S200) corresponds to adding a starting material to the first material 100 and the second material 200 and heating them.

The heating step (S200) according to an embodiment of the present invention includes a first step of adding an initiator that induces a radical chain reaction in a mixture of the first material and the second material. do.

That is, in the first step, a starting material that acts as a catalyst to start the reaction is added to the first material 100 and the second material 200 mixed in the mixing step (S100), and then heated to form a third material. Material 300 is created.

According to one embodiment of the present invention, preferably, the first material 100 may be fluorinated acrylate, and the second material 200 may be preferably polyfunctional urethane acrylate ( Multi-functional urethane acrylate).

Additionally, in this case, the starting material may be AIBN (Azobisisobutyronitrile).

Additionally, the heating step (S200) according to an embodiment of the present invention includes a second step of heating the first material, the second material, and the starting material at a temperature of 50 to 100°C.

In the heating step according to an embodiment of the present invention, the first material 100 and the second material 200 react continuously by heat, so that the third material 300 formed by the reaction becomes a macromolecule. It has a gel form, and in the ultrasonic treatment step (S300), the third material 300 is converted from a gel form to a liquid form to form a coating layer.

For example, in the heating step (S200), fluorinated acrylate, multi-functional urethane acrylate, and AIBN (Azobisisobutyronitrile) are placed in a beaker and heated to a temperature of 50 to 100° C. on a hot plate. Heat with .

At this time, the heating temperature may preferably be between 60 and 90°C.

More preferably, the temperature may be 75 to 85°C.

Meanwhile, the heating time may preferably be 10 minutes or more.

More preferably, it may be 20 minutes or more until the liquid third material is completely gelled.

Through this process, the third material 300 can be produced, and in one embodiment of the present invention, the third material 300 may be a fluro-rich acrylate oligomer.

The first material 100 according to an embodiment of the present invention includes fluorinated acrylate, and the second material 200 includes multi-functional urethane acrylate. In the heating step (S200), heating is performed with the addition of a radical initiator that induces a radical chain reaction, thereby forming a portion of the acrylate site of the polyfunctional urethane acrylate and fluorination. The acrylate site of the acrylate reacts, and another part of the acrylate site of the multifunctional urethane acrylate may not participate in the polymerization with the fluorinated acrylate.

In addition, the third material 300 after the heating step according to an embodiment of the present invention is composed of a portion of the acrylate site of the multifunctional urethane acrylate and the acrylate of the fluorinated acrylate. Site-reacted multifunctional urethane acrylate oligomer; And it may include the fluorinated acrylate that does not participate in the reaction.

The ultrasonic treatment step (S300) corresponds to the step of sonicating the third material formed from the first material and the second material on which heating was performed.

In the heating step (S200), when heat is continuously applied and the reaction is maintained without stopping, the third material 300, which was initially liquid, may gel over time. This is because the third material 300 has become a macromolecule due to a continuous reaction, and the gelated third material 300 has characteristics that make it difficult to form a thin film, so it may be difficult to use it as the low-reflection coating material. In the ultrasonic treatment step (S300) of sonicating the third material 300 made by heating the first material 100 and the second material 200, the third material 300 is gelled by ultrasonic treatment. can be liquefied again.

Ultrasonic treatment uses a device called a sonicator.

For example, a solvent can be mixed with gelled Fluro-rich acrylate oligomer and sonicated using a sonicator.

The ultrasonic treatment may proceed until the third material 300 is completely liquefied, and may preferably take more than three hours.

Meanwhile, the solvent according to an embodiment of the present invention may preferably be 1-methoxy-2-propanol (PGME, Propyleneglycol methyl ether).

In the ultrasonic treatment step (S300) according to an embodiment of the present invention, the third material gelled in the heating step is sonicated and liquefied using ultrasonic waves and heat generated during the ultrasonic treatment process. there is.

In one embodiment of the present invention, in the ultrasonic treatment step (S300), the third material 300 in the form of a gel is placed in an appropriate container such as a vial, and when the sonicator is operated, the ultrasonic waves generated from the sonicator are applied. The third material 300 in the form of a gel may be liquefied by the heat generated by the shock and ultrasonic waves generated from the sonicator. More specifically, the ultrasonic treatment time is 3 hours, and at this time, the temperature of the third material 300 can rise to 50°C.

The coating material manufacturing step (S400) is a step of mixing and then stirring the third material 300, the high refractive index material 400, and the UV curable urethane binder 500 that have undergone the ultrasonic treatment, through the ultrasonic treatment. The low-reflection coating material is manufactured by mixing the liquefied third material 300, which is a low-refractive material, with the high-refractive material 400, the UV-curable urethane binder 500, and a solvent.

In the coating material manufacturing step (S400), the third material 300 on which ultrasonic treatment (S300) was performed, the high refractive material 400 having a higher refractive index than the third material 300, and the UV curable urethane binder 500 ) After mixing, stirring can be performed to produce a coating material.

The solvent according to an embodiment of the present invention may preferably be 1-methoxy-2-propanol (PGME, Propyleneglycol methyl ether).

The high refractive index material 400 according to an embodiment of the present invention may preferably be ZrO ₂ dispersed fluorene acrylate or fluorene acrylate, and the UV curable urethane binder 500 may be a photo-curable multi-functional urethane acrylate oligomer. there is. More specifically, it may be SC2152 (brand name, manufacturer: Miwon specialty chemical, Korea).

The detailed mixing ratio of the above materials will be described later.

That is, the present invention can produce a low-reflection coating material through the mixing step (S100), the heating step (S200), the ultrasonic treatment step (S300), and the coating material manufacturing step (S400). The low-reflection coating material includes the third material 300, the high refractive index material 400 in which metal oxide such as ZrO2 is uniformly dispersed, and the UV curable urethane binder 500 such as photo-curable multi-functional urethane acrylate oligomer. ) When the low-reflection coating layer 600 is formed using mixed materials and then heat is applied, the low-reflection coating layer 600 in which a refractive index gradient is formed in a single layer can be manufactured.

According to an embodiment of the present invention, the high refractive index material 400 may be ZrO ₂ dispersed fluorene acrylate and Fluorene acrylate.

In one embodiment of the present invention, the coating layer formed by UV curing of the coating material is dispersed entirely in the UV-curable urethane binder 500 and is coated with the third material 300 due to a difference in surface tension. ) may be located on the upper side, and the high refractive index material 400 may be located on the lower side. That is, an overall refractive index gradient may be formed by a concentration gradient generated according to a difference in surface tension between the third material, which is a low-refractive material, and the high-refractive material.

More specifically, in one embodiment of the present invention, the low-reflection coating layer 600 is predominantly composed of fluorinated-oligomers, which are molecules with low refractive properties, in the area close to the surface, and in the lower layer, high refractive properties such as ZrO _2. Molecules with are dominantly disposed, so a concentration gradient may occur between the low refractive index material and the high refractive index material. In this state, when the low-reflection coating layer 600 is UV-cured, it is formed as a single layer and may include a refractive index gradient formed as a whole by the concentration gradient.

In this way, in one embodiment of the present invention, the effect of implementing a single-layer low-reflection coating can be achieved by using a concentration gradient using the difference in surface tension between the low refractive index material and the high refractive index material.

That is, the low-reflection coating layer 600 according to an embodiment of the present invention corresponds to a single-layer structure coating layer with sufficient strength and hardness.

FIG. 2 conceptually illustrates a first material 100, a second material 200, and a third material 300 according to an embodiment of the present invention.

FIG. 2A conceptually illustrates the first material 100, and FIG. 2(B) conceptually illustrates the second material 200.

As shown in FIG. 2A, the first material 100 is made of fluorite 110 and acrylate site 120 connected to each other. As shown in FIG. 2B, the second material is composed of fluorite 110 connected to each ring around a carbon chain 210.

More specifically, when mixing the first material 100 and the second material 200, the first material 100 may preferably be fluorinated acrylate.

[Formula 1]

More specifically, it may be 1H,1H,5H-Octafluoropentyl Methacrylate, and the detailed molecular structure is as shown in [Chemical Formula 1].

[Formula 2]

At this time, [Formula 2], which is part of [Formula 1], is acrylate site 120, which may correspond to 120 in FIG. 2A.

[Formula 3]

Additionally, [Formula 3] is fluorite 110 and may correspond to 110 in FIG. 2A.

Additionally, as shown in FIG. 2A, fluorinated acrylate may be in a form in which two acrylate sites 120 exist, one on each side of the fluorite site 110.

As shown in [Formula 1], the presence of one acrylate site 120 is called a fluorinated acrylate monomer, and there is one acrylate site 120 on both sides of the fluorite 110, The two forms that exist in total are called fluorinated acrylate dimers.

Additionally, the second material 200 may preferably be multi-functional urethane acrylate.

Figure 2C conceptually shows the third material 300 synthesized from the first material 100 and the second material 200.

As described above, the first material 100 and the second material 200 undergo a heating step (S200), and the first material 100 and the second material are mixed in the mixing step (S100). A starting material that acts as a catalyst to start the reaction is added to (200) and then heated to produce the third material (300) in the same form as shown in FIG. 2C. At this time, the starting material is a material that induces free radical polymerization of the first material 100 and the second material 200, and during the heating step (S200), the first material 100 and the second material ( 200), and the starting material is heated at a temperature of 50 to 100° C., thereby allowing free radical polymerization to occur.

At this time, the starting material is separated into nitrogen gas (N ₂ ) and two molecules of isobutylnitrile radical by heat or ultraviolet rays according to the reaction shown in [Chemical Formula 4] below.

[Formula 4]

This radical has one electron and is therefore very unstable. Therefore, since it tries to achieve a stable state by accepting one electron, it tries to react immediately if there is an electron nearby that can be shared.

전자들은 이 자유라디칼과 쉽게 반응할 수 있다. 라디칼이 이중결합 근처로 오면 이중결합에 있는 전자 하나가 라디칼과 반응하게 된다. C=C double bond in vinyl monomers such as ethylene

Electrons can easily react with these free radicals. When a radical comes near a double bond, one electron in the double bond reacts with the radical.

In this way, the radical generated when the initiator is decomposed by an external stimulus attacks the vinyl monomer, and the process of forming a new radical containing one monomer molecule is called initiation.

[Formula 5]

As in the example of [Formula 5], monomer radicals are also not stable, so they cause the same reaction. A new monomer binds, the radical is transferred to a new end, and this reaction is repeated, allowing the chain to grow in length. This is called a radical chain reaction, which is one of the reactions that occurs during free radical polymerization. As shown in FIG. 2, the first material 100 and the second material 200 may be formed into the third material 300 through the radical chain reaction.

Through this process, the third material 300 can be produced,

The third material 300 is formed by reacting the acrylate sites 120 of the second material 200 with the acrylate sites 120 of the first material 100 through the radical chain reaction. Some of the acrylate sites 120 of the second material 200 may be replaced with the fluorosite 110.

According to one embodiment of the present invention, as shown in FIG. 2, the fluorinated acrylate is mixed with the multi-functional urethane acrylate, and the starting material AIBN (Azobisisobutyronitrile) is added thereto. ) is added and heat energy is applied, as shown in Figure 2, part of the acrylate site 120 of the multi-functional urethane acrylate and the acrylate site of the fluorinated acrylate monomer (120) may react and some of the acrylate sites 120 of the multi-functional urethane acrylate may remain without participating in polymerization.

That is, the third material 300, which is the result of the reaction shown in FIG. 2, is a part of the fluorinated acrylate monomer and multi-functional urethane acrylate that did not participate in the reaction. Oligomers in which latesite (120) is combined with fluorite (110) may coexist.

In such a reaction, when heat is continuously applied and the reaction is maintained without stopping, the third material 300, which was initially liquid, may turn into a gel over time.

Preferably, the heating step (S200) according to an embodiment of the present invention is a third step in which a liquid reactant is generated by heating the first material, the second material, and the starting material for 10 to 30 minutes. ; And after performing the third step, a fourth step of additionally heating the liquid reactant until the liquid reactant is converted into macromolecules and takes the form of a gel; including the third step and the third step. Step 4 can be performed sequentially.

The liquid reactant corresponds to the third material 300.

In one embodiment of the present invention, the third and fourth steps may be performed for 1 to 4 hours.

Preferably, the process can be continued until the third material turns into a gel.

In this configuration, the third material 300 can be macromolecularized into a gel.

The gelled third material 300 has characteristics that make it difficult to form a thin film, so it may be difficult to use as the low-reflection coating material. However, it is made by heating the first material 100 and the second material 200. If the third material 300 is subjected to ultrasonic treatment in the ultrasonic treatment step (S300), the gelled third material 300 can be liquefied again.

Preferably, in the ultrasonic treatment step (S300) according to an embodiment of the present invention, the third material 300 gelled in the heating step (S200) is sonicated, and the ultrasonic and ultrasonic treatment process is performed. It can be liquefied using the heat generated from it.

More specifically, when heating the first material 100 and the second material 200 to produce the third material 300, they are reacted for an appropriate amount of time (may vary depending on the amount of material). When the third material 300 is in a liquid form, by lowering the temperature, the two growing radicals are combined to form electron pairs, thereby removing the radicals and stopping the reaction.

Meanwhile, the appropriate time according to an embodiment of the present invention is 30 to 60° C. at a temperature of 75 to 85° C. when the amount of the first material 100 is 8 g and the amount of the second material 200 is 8.4 g. It can be minutes.

On the other hand, if the temperature is not lowered, the reaction continues to occur, and at this time, the third material 300 continues to increase in molecular weight through the radical chain reaction and may become a macromolecule.

In this way, the macromolecularized third material 300 can gradually change from a liquid state to a gel form. The macromolecularized third material 300 exhibits excellent low refractive index material properties, but may be difficult to form into a thin film due to its gel properties.

Meanwhile, the third material 300 according to an embodiment of the present invention is operated at a temperature of 75 to 85° C. when the amount of the first material 100 is 8 g and the amount of the second material 200 is 8.4 g. It can be heated for 3 to 4 hours, and preferably, the third material 300 can be gelled through the third and fourth steps.

Therefore, the gelled third material 300 must be liquefied to make it easy to form into a thin film, and for this purpose, an ultrasonic treatment step (S300) can be used.

Figure 3 schematically shows the high refractive index material 400 and the UV-curable urethane binder 500 according to an embodiment of the present invention.

Figure 3A schematically shows the high refractive index material 400 according to an embodiment of the present invention.

The high refractive index material 400 according to an embodiment of the present invention may preferably be ZrO ₂ dispersed fluorene acrylate or Fluorene acrylate. The high refractive index material 400 may include the acrylate site 120 and fluorensite 410 in the carbon chain 210, and may further include a metal oxide.

The metal oxide according to an embodiment of the present invention may preferably be ZrO ₂ .

The high refractive material 400 according to an embodiment of the present invention is an acrylate with the fluorensite 410, and has a three-dimensional and bulky cardo structure, so it can have chemical properties not found in existing acrylates. These properties may include a high refractive index of 1.6 or more after curing, high heat resistance, low curing shrinkage, high flexibility, heat resistance to yellowing, heat resistance stability, and scratch resistance.

These characteristics of the high refractive index material 400 can provide various properties required for the single-layer thin film for the low-reflection coating layer 600.

Figure 3B schematically shows the UV-curable urethane binder 500 according to an embodiment of the present invention.

The UV-curable urethane binder 500 according to an embodiment of the present invention may be a UV-curable high-hardness urethane binder that is cured to high hardness by UV light, and may preferably be a photo-curable muti-functional urethane acrylate oligomer. .

More specifically, the UV-curable urethane binder 500 contains acrylate and can serve as a binder to bind the third material 300 and the high refractive material 400, and has photo-curable properties. Because it is cured through UV light, the third material 300 and the high refractive material 400, which are molded in a thin film form, can be fixed in a thin film form to form a coating layer. A more detailed description of this will be provided later with reference to FIG. 4 .

Figure 4 schematically shows a cross section of the low-reflection coating layer 600 according to an embodiment of the present invention.

The low-reflection coating material according to an embodiment of the present invention includes the third material 300, which is a low refractive material, the high refractive material 400, and the UV curable urethane binder 500, and the low refractive material. A low-reflection single layer in which an overall refractive index gradient is formed by the concentration gradient generated according to the difference in surface tension of the third material 300, the high refractive material 400, and the UV curable urethane binder 500. A coating layer can be manufactured.

The low-reflection coating layer 600 according to an embodiment of the present invention is the low-reflection coating material including the third material 300, the high refractive material 400, the UV curable urethane binder 500, and a solvent. It can be formed through.

More specifically, the weight ratio of the low-reflection coating material to the low-reflection coating material made by mixing the third material 300, the high refractive material 400, the UV curable urethane binder 500, and the solvent corresponds to 0.7%. benzophenone, 1-Hydroxy-cyclohexyl-phenyl-ketone corresponding to 0.7% by weight of low-reflection coating material, and 2-Hydroxy-1-[4-[4-(2-) corresponding to 1.4% by weight of low-reflection coating material. Mix hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methoxypropane-1-one and stir until completely dissolved. The stirred mixture can be used to form a coating film on the surface of a 100㎛ thick PMMA (polymethylmethacrylate) film using Mayer bar #3, then dried in a convection oven at 100°C, and then UV cured with a light quantity of 400mJ/cm ² .

During drying in a convection oven at 100°C, the solvent may evaporate and disappear.

In one embodiment of the present invention, benzophenone, 1-Hydroxy-cyclohexyl-phenyl-ketone and 2-Hydroxy-1-[4-[4-(2) are used to form the low-reflection coating layer 600 using the low-reflection coating material. -hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methoxypropane-1-one was used, but this may be changed by referring to previously disclosed technologies depending on the purpose of coating or the material of the surface to be coated.

Mayer bar and PMMA film are widely known technologies, so detailed descriptions will be omitted.

Figure 4 schematically shows the molecular structure of the cross section of the low-reflection coating layer 600 formed on the PMMA film through this process.

As shown in FIG. 4, the third material 300, which is a low refractive material, is predominantly disposed in the upper layer area close to the surface of the low-reflection coating layer 600, and the high refractive material material is disposed in the lower layer area away from the surface of the thin film. As (400) is dominantly disposed, a concentration gradient occurs between the third material (300) and the high refractive index material (400).

More specifically, when the low-reflection coating material is formed as a thin film on the surface of the PMMA film using a Mayer bar, the third material 300 and the UV-curable urethane binder 500 receive heat energy applied by the convection oven and mix. In this situation, the third material 300 moves toward the air layer due to the difference in surface tension between the third material 300 and the UV-curable urethane binder 500, and the upper layer of the thin film in contact with the air is the third material ( 300) may be the dominant concentration.

In addition, all solvents are evaporated by the heat of the convection oven, and when UV light is applied to the third material 300, the UV curable urethane binder 500, and the high refractive material 400 remaining in the thin film, the UV curable urethane binder Due to the UV curing properties of (500), the thin film is hardened and the low-reflection coating layer (600) can be implemented.

The low-reflection coating layer 600 formed through this method is a single layer, but a concentration gradient of the third material 300 and the high refractive index material 400 exists inside the single layer, and the refractive index formed by this concentration gradient A low-reflection coating effect can be realized by exhibiting an effect equivalent to the low-reflection coating layer 600 of an existing multilayer thin film in which a low refractive index thin film and a high refractive index thin film are stacked in multiple layers according to a gradient as a single layer.

In addition, the UV-curable urethane binder 500 evenly spread inside the low-reflection coating layer 600 can provide sufficient hardness, wear resistance, scratch resistance, and anti-fingerprint properties to be used in fields such as automotive displays.

Hereinafter, an experiment related to the reflectance of the low-reflection coating layer 600 formed by the low-reflection coating material according to an embodiment of the present invention will be described in detail.

In this experiment, in order to compare and confirm the low-reflection effect of the conventional technology and the present invention, an experiment was conducted to compare the following five examples.

The above experiment is an experiment in which a gel-like is formed in the synthesis stage of a low-refractive index polymer, then the gel-like is formed again by applying sonification and heat to proceed with final mixing, and an experiment is performed in which a gel-like is not formed in the synthesis stage of a low-refractive polymer. , experiments conducted by mixing all materials in one-pot without synthesizing low-refractive index polymers, and experiments in which the materials of each experiment were changed were included.

In this experiment, the following materials were used.

First substance (100)

First substance #1: 1H,1H,5H-Octafluoropentyl Methacrylate (Brand name: O0481, Manufacturer: TCI, Japan)

Refractive index: 1.36

First substance #2: 1H,1H,2H,2H-Tridecafluoro-n-octyl Acrylate (Brand name: T3451, Manufacturer: TCI, Japan)

Refractive index: 1.34

First substance #3: SFA420 (brand name, manufacturer: SHIN-A T&C, Korea)

Fluorinated hexa-functional urethane acrylate oligomer

Refractive index: 1.419

First substance #4: SFA335 (brand name, manufacturer: SHIN-A T&C, Korea)

Fluorinated di-functional urethane acrylate oligomer

Refractive index: 1.335

High refractive index material (400)

High refractive index material #1: SHO H6500 (brand name, manufacturer: SHIN-A T&C, Korea)

ZrO ₂ dispersed fluorene acrylate

Refractive index: 1.642

High refractive index material #2: OGSOL EA-0250P (brand name, manufacturer: OSAKA GAS CHEMICAL, Japan)

Fluorene acrylate

Refractive index: 1.626

Second substance (200)

SC2152 (brand name, manufacturer: Miwon specialty chemical, Korea)

solvent

1-methoxy-2-propanol (PGME, Propyleneglycol methyl ether)

starting material

Azobisisobutyronitrile (AIBN), Use by dissolving in 8wt% in methanol

Examples of the low-reflection coating material in this experiment are as follows.

Example 1

Mix 1st substance #1: 16.04g, 1st substance #3: 0.633g, 2nd substance: 0.38 and solvent: 28g and stir until all ingredients are completely dissolved.

Mix 2 g of starting material (AIBN, 8 wt% in methanol) in the above solution and heat on a hot plate (set temperature of 80°C for 20 minutes. After 20 minutes, stop heating and cool at room temperature for 10 minutes. The cooled result is a gel. The cooled result may be sonicated for 3 hours.

Mix low refractive material sonicated for 3 hours: 6.43g, high refractive material #1: 1.025g, high refractive material #2: 0.625g, UV curable urethane binder 1.25g, and solvent: 21.7g and stir to form a uniform mixture. [ 4-[4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methoxypropane-1-one can be mixed and stirred until completely dissolved.

The final mixture can be used to form a coating film on the surface of a 100㎛ thick PMMA (polymethylmethacrylate) film using Meyer bar #3, dried at 100°C, and then UV cured with a light dose of 400mJ/cm ² .

The low-reflection coating layer 600 manufactured in this manner is named Example 1.

Example 2

Mix 1st substance #1: 16.04g, 1st substance #3: 0.633g, 2nd substance: 0.38g and solvent: 28g and stir until all ingredients are completely dissolved.

Mix 2 g of starting material (AIBN, 8 wt% in methanol) in the above solution and heat on a hot plate (set temperature of 80°C for 10 minutes. After 10 minutes, stop heating and cool at room temperature for 10 minutes.

Mix cooled low refractive material: 13.5g, high refractive material #1: 1.03g, high refractive material #2: 0.62g, UV curable urethane binder: 1.25g, solvent: 21.7g and stir to form a uniform mixture. [ Mix 4-[4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methoxypropane-1-one and stir until completely dissolved.

The final mixture is used to form a coating film on the surface of a 100㎛ thick PMMA (polymethylmethacrylate) film using Meyer bar #3, dried at 100℃, and then UV cured with a light dose of 400mJ/cm ² .

The low-reflection coating layer 600 manufactured in this manner is named Example 2.

Example 3

Example 3 (Recipe #7)

Mix 1st substance #2: 3.25g, 1st substance #3: 0.8g, 2nd substance: 14g and solvent: 23g and stir until all ingredients are completely dissolved.

Mix 5.5 g of starting material (AIBN, 8 wt% in methanol) in the above solution and heat on a hot plate (set temperature of 80°C for 10 minutes. After 10 minutes, stop heating and cool at room temperature for 10 minutes.

Mix cooled low refractive material: 9.0g, high refractive material #1: 0.2g, high refractive material #2: 0.1g, UV curable urethane binder: 1.5g, solvent: 10.0g and stir to form a uniform mixture. [ Mix 4-[4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methoxypropane-1-one and stir until completely dissolved.

The final mixture is used to form a coating film on the surface of a 100㎛ thick PMMA (polymethylmethacrylate) film using Meyer bar #3, dried at 100°C, and then UV cured with a light dose of 400mJ/cm ² .

The low-reflection coating layer 600 manufactured in this manner is named Example 3.

Example 4

Mix first material #4: 18.07g, second material: 0.88g, and solvent: 28.52g and stir until all materials are completely dissolved.

Mix 19.29g of the above mixture with high refractive material #1: 1.03g, high refractive material #2: 0.63g, UV curable urethane binder: 1.25g, and solvent: 21.7g and stir to form a uniform mixture. In the stirred mixture, benzophenone corresponding to 0.7% by weight of the mixture solid content, 1-Hydroxy-cyclohexyl-phenyl-ketone corresponding to 0.7% by weight of the mixture solid content, and 2-Hydroxy-1-[ corresponding to 1.4% by weight of the mixture solid content. Mix 4-[4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methoxypropane-1-one and stir until completely dissolved.

The final mixture is used to form a coating film on the surface of a 100㎛ thick PMMA (polymethylmethacrylate) film using Meyer bar #3, dried at 100°C, and then UV cured with a light dose of 400mJ/cm ² .

The low-reflection coating layer 600 manufactured in this manner is named Example 4.

Example 5

Mix 1st substance #1: 9.6g: 16.04g, 1st substance #3: 0.0.38g, 2nd substance: 0.23 and solvent: 16.8g and stir until all ingredients are completely dissolved.

Mix the starting material (AIBN, 8 wt% in methanol): 1.2 g with the above solution and heat on a hot plate (set temperature of 80°C for 20 minutes. After 20 minutes, stop heating and cool at room temperature for 10 minutes.

Mix the cooled low refractive material: 6.43g, high refractive material #1: 1.025g, high refractive material #2: 0.625g, UV curable urethane binder: 1.25g, and solvent: 21.7g and stir to form a uniform mixture. [ Mix 4-[4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methoxypropane-1-one and stir until completely dissolved.

The final mixture is used to form a coating film on the surface of a 100㎛ thick PMMA (polymethylmethacrylate) film using Meyer bar #3, dried at 100°C, and then UV cured with a light dose of 400mJ/cm ² .

The low-reflection coating layer 600 manufactured in this manner is named Example 5.

Example 1 Example 2 Example 3 Example 4 Example 5 Whether thermal synthesis is in progress progress progress progress Not in progress progress Morphology of low-refractive thermosynthesis results Gel-like Liquid Liquid - Liquid Post-processing of low refractive index thermosynthesis results Sonification & heat 3 hours - - - -

Table 1 is an easy-to-understand table of the methods for synthesizing low-refractive materials according to each example. Example 1, in which a low-refractive index material in the form of a gel was made through thermal synthesis and ultrasonic treatment, is the method of the present invention. It can be seen that it is the third material 300.

Black ink was applied to the opposite side of the coated surface of the low-reflection coating layer 600 (Example 1, Example 2, Example 3, Example 4, and Example 5) made in this way, and after drying, each was measured using a spectrophotometer. The reflectance of the examples can be measured.

Example 1 Example 2 Example 3 Example 4 Example 5 Reflectance@550nm 1.67% 2.8% 3.81% 5.16% 6.28% Water contact angle 94.2 degrees - 101.58 degrees - -

Table 2 shows the reflectance for the 550 nm wavelength of each Example. It can be seen that the reflectance of Example 1, which is the method of the present invention, is the lowest, and the water contact angle of Example 3 is the water contact angle of Example 1. It can be seen that there is a greater secondary effect.

Figure 5 is a graph measuring the reflectance in the visible light range of 350 to 750 nm for Examples 1, 2, 3, 4, and 5, and PMMA films without the low-reflection coating layer 600. It is compared and expressed as .

As shown in Figure 5, it can be seen that Example 1 manufactured according to the method of the present invention exhibits the lowest reflectance throughout the visible light region.

According to one embodiment of the present invention, the effect of implementing the low-reflection coating layer 600 as a single layer can be achieved by using a concentration gradient using the difference in surface tension between the low-refractive index material and the high-refractive index material.

According to one embodiment of the present invention, by implementing the low-reflection coating layer 600 as a single layer, it is possible to achieve the effect of implementing a low-reflection layer with high hardness.

According to one embodiment of the present invention, by implementing the low-reflection coating layer 600 as a single layer, functionality such as anti-fingerprint and scratch resistance can be improved.

According to one embodiment of the present invention, the hardness can be improved by UV curing the coating using the UV curing property of the binder.

According to one embodiment of the present invention, the effect of turning the synthetic reactant into a macromolecule can be achieved by synthesizing the reaction time long enough to gel.

According to one embodiment of the present invention, the gelled reactant can be liquefied by ultrasonic treatment to achieve the effect of using it as a low refractive index material that can be formed into a thin film.

According to one embodiment of the present invention, by converting the synthesis reactants into macromolecules, it is possible to exhibit a low-reflection effect superior to that of the conventional single-layer low-reflection coating layer 600.

The description of the presented embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments without departing from the scope of the invention. Thus, the present invention is not limited to the embodiments presented herein, but is to be construed in the broadest scope consistent with the principles and novel features presented herein.

100: first substance
110: fluorite
120: Acrylate site
200: Second substance
210: carbon chain
300: Third substance
400: High refractive index material
410: fluorensite
500: UV curable urethane binder
600: Low-reflective coating layer

Claims (7)

As a method of manufacturing a low-reflection coating material,
A mixing step of mixing a first material containing an acrylate and a second material containing a multifunctional acrylate;
A heating step of heating the mixed first material and the second material;
An ultrasonic treatment step of sonicating a third material formed by heating the first material and the second material; and
A coating material manufacturing step of mixing the third material on which ultrasonic treatment was performed, a high refractive index material having a higher refractive index than the third material, and a UV-curable urethane binder and then stirring to produce a coating material. Method of manufacturing reflective coating material.
In claim 1,
The heating step is,
A first step of adding a radical initiator to induce a radical chain reaction in a mixture of the first material and the second material; and
A method of manufacturing a low-reflection coating material comprising; a second step of heating the first material, the second material, and the starting material at a temperature of 50 to 100°C.
In claim 1,
In the heating step, the first material and the second material react continuously by heat, so that the third material formed by the reaction becomes macromolecules and takes the form of a gel,
In the ultrasonic treatment step, the third material is converted from a gel form to a liquid form to form a coating layer.
In claim 1,
The first material includes fluorinated acrylate,
The second material includes multi-functional urethane acrylate,
In the heating step, heating is performed with the addition of a radical initiator that induces a radical chain reaction, thereby forming a portion of the acrylate site of the multifunctional urethane acrylate and the acrylate of the fluorinated acrylate. A method of manufacturing a low-reflection coating material in which the site reacts, and another part of the acrylate site of the multifunctional urethane acrylate does not participate in polymerization with the fluorinated acrylate.
In claim 4,
The third material after the heating step is performed,
A polyfunctional urethane acrylate oligomer obtained by reacting a portion of the acrylate site of the polyfunctional urethane acrylate with an acrylate site of the fluorinated acrylate; and
A method of producing a low-reflection coating material comprising the fluorinated acrylate that does not participate in the reaction.
In claim 1,
The coating layer formed by UV curing of the coating material is,
While dispersed entirely in a UV-curable urethane binder,
A method of manufacturing a low-reflection coating material in which the third material is located on the upper side and the high refractive material is located on the lower side due to a difference in surface tension.
In claim 6,
The coating layer formed by UV curing of the coating material is,
A method of manufacturing a low-reflection coating material in which an overall refractive index gradient is formed by a concentration gradient generated according to a difference in surface tension between the third material, which is a low-refractive material, and the high-refractive material.