KR20210060133A - Coating Apparatus and manufacturing method of the Optical layer using the same - Google Patents

Abstract

The present invention relates to a coating apparatus and a method for manufacturing an optical laminate using the same. More specifically, the present invention relates to: a coating apparatus which can real-time monitor the properties of a coating thin film, and thus can secure the uniformity of the coating thin film and reproducibility of the properties of a thermochromic thin film by controlling the coating process parameters in real time; and a method for manufacturing the optical laminate using the same.

Description

Coating apparatus and manufacturing method of optical laminate using the same {Coating Apparatus and manufacturing method of the Optical layer using the same}

The present invention relates to a coating apparatus and a method of manufacturing an optical laminate using the same, and in particular, by controlling the coating process parameters in real time through real-time monitoring of the coating thin film properties, it is possible to ensure uniform coating thin film and reproducibility of thermochromic thin film properties. It relates to a possible coating device and a method of manufacturing an optical laminate using the same.

A thermochromic glass is being studied that controls the inflow of energy through infrared transmittance control by coating a thermochromic layer having thermochromism on glass.

Thermochromic is a phenomenon in which the color of an oxide or sulfide of a certain transition metal changes reversibly at a transition temperature (or critical temperature). It is possible to manufacture a thermochromic glass that does not increase the indoor temperature by blocking near-infrared rays and infrared rays. By using this characteristic, it is possible to shield near-infrared light at high temperatures in summer to suppress an increase in indoor temperature, and to bring light energy from outside at low temperatures in winter. If such thermochromic glass is used for windows and doors of buildings, great energy savings can be expected.

Korean Patent Registration No. 10-1955207 discloses an optical laminate including an organic-inorganic hybrid thermochromic layer and a method for manufacturing the same, and forming a coating layer by applying a solution containing vanadium oxide particles on a substrate, applying Disclosed is a method of manufacturing an optical laminate comprising the step of removing the solvent from the layer and photo-sintering the vanadium oxide particles contained in the coating layer.

For a large area, in order to maintain the coating thin film uniformly and to secure the reproducibility of the thermochromic thin film characteristics, it is necessary to monitor the characteristics of the thin film during the coating process and control the parameters of the coating process.

The present invention is to provide a coating apparatus capable of securing a coating thin film uniformity and reproducibility of thermochromic thin film characteristics by controlling a coating process variable in real time through real-time monitoring of a coating thin film characteristic, and a method of manufacturing an optical laminate using the same. Make it the task to be solved.

In order to solve the above problems, according to an aspect of the present invention, a nozzle unit including an ink ejection unit and a deflector receiving ink from the ink supply unit, a transfer unit for moving the nozzle unit during ink injection, and formed of the jetted ink. A measurement unit for measuring thin film properties and a control unit for controlling the nozzle unit and the transfer unit based on the measured result of the measurement unit, and the control unit determines the spray distance when the measured area of the thin film is out of a predetermined area range. When the measured thin film area is within a predetermined area range, a coating device is provided to compare whether or not the measured thin film thickness is within a predetermined thickness range, and when the measured thin film thickness is out of a predetermined thickness range, a coating device provided to control the ink injection amount is provided. Is provided.

In addition, according to another aspect of the present invention, as a method of manufacturing an optical laminate using the coating device, an ink containing vanadium oxide particles is applied on a substrate to provide a predetermined thin film area, thin film thickness, surface roughness and thickness uniformity. Including the step of forming a coating layer having, in the step of forming the coating layer, when the measured thin film area is out of the predetermined area range, the spray distance is adjusted, and the measured thin film area is within the predetermined area range , Comparing whether or not the measured thin film thickness is within a predetermined thickness range, and when the measured thin film thickness is out of the predetermined thickness range, there is provided a method of manufacturing an optical laminate comprising the step of adjusting an ink ejection amount.

As described above, according to the coating apparatus related to at least one embodiment of the present invention and the manufacturing method of the optical laminate using the same, by controlling the coating process parameters in real time through real-time monitoring of the properties of the coating thin film, uniform coating thin film And it is possible to secure the reproducibility of the thermochromic thin film characteristics.

1 is a block diagram showing a coating apparatus according to an embodiment of the present invention.
2 is a flowchart showing a method of manufacturing an optical laminate according to an embodiment of the present invention.

Hereinafter, a coating apparatus according to an embodiment of the present invention and a method of manufacturing an optical laminate using the same will be described in detail with reference to the accompanying drawings.

In addition, regardless of the reference numerals, the same or corresponding components are given the same or similar reference numbers, and redundant descriptions thereof will be omitted, and the size and shape of each component member shown for convenience of explanation are exaggerated or reduced. Can be.

1 is a block diagram showing a coating apparatus 1 related to an embodiment of the present invention, and FIG. 2 is a flowchart showing a method of manufacturing an optical laminate according to an embodiment of the present invention.

The coating apparatus 1 related to an embodiment of the present invention is a spray coating apparatus 1, and may be an ultrasonic nozzle spray coating apparatus 1.

Referring to FIG. 1, the coating apparatus 1 includes a nozzle unit 20, a transfer unit 30, a measurement unit 40, and a control unit 50.

In this document, ink means a solution composition containing vanadium oxide, and the solution composition containing vanadium oxide may include vanadium oxide particles, a solvent, a polymer dispersant, and a binder. have. In one embodiment, the vanadium oxide particles may include rutile type vanadium dioxide (VO2) particles. The content of the vanadium dioxide particles is, for example, 1 to 50% by weight, for example 5 to 40% by weight, 10 to 35% by weight, 15 to 30% by weight based on the total weight of the solution composition. In addition, the average diameter of the vanadium dioxide particles may be 1 to 1000 nm, for example, 10 to 500 nm, and when the vanadium dioxide particle content and the average diameter are controlled within the above range, excellent thin film formation, uniform dispersibility and desired functionality can be obtained. . The solution composition may be prepared by mixing vanadium dioxide particles, a polymer dispersant, and a binder in a solvent, and stirring uniformly. The method of preparing a solution composition (ink) includes preparing a polymer dispersant solution by mixing a polymer dispersant with a first solvent, preparing a binder solution by mixing a binder with a second solvent, and the polymer dispersant solution in vanadium dioxide particles. And preparing an ink solution by mixing a binder solution and optionally or optionally further mixing a dopant.

Ultrasound may be applied to the solution for uniform dispersion of the solution prepared in each step. For example, the manufacturing method may further include one or more steps from the group consisting of applying ultrasonic waves to a polymer dispersant solution, applying ultrasonic waves to a binder solution, and applying ultrasonic waves to an ink solution. . The ultrasonic application conditions are not particularly limited, but may be applied for 30 minutes to 2 hours in each step.

In the above step, the first solvent and the second solvent may be used without limitation as long as they are solvents capable of dissolving a dispersant and a binder, respectively. For example, water may be used as the first solvent and ethanol may be used as the second solvent.

Meanwhile, the coating apparatus 1 includes a nozzle unit 20 including an ink ejection unit and a deflector receiving ink from the ink supply unit 10. The nozzle unit 20 performs a function of spraying ink supplied from the ink supply unit 10 and applying the ink onto the substrate. The nozzle unit 20 may include an ink ejection portion through which ink is ejected, and the ink ejection portion may be configured by an ultrasonic spray method. In addition, the deflector applies an air flow toward the ink ejection portion to adjust the ejection pattern (shape, etc.) of the ink ejected from the ink ejection portion. Specifically, the deflector performs a function of collecting ink particles falling from the ultrasonic nozzle, and includes gas injection ports respectively located on both sides of the ink injection unit. At this time, the gas injection port is provided to inject gas toward the ink particles falling from the ultrasonic nozzle. When the deflector flow rate is increased, ink particles falling from the nozzle are further atomized and are induced to be sprayed over a large area. On the contrary, when the deflector flow rate decreases, the spray area falling from the nozzle becomes narrower, and the thin film thickness increases.

In addition, the coating apparatus 1 may include a transfer unit 30 for moving the nozzle unit 20 when spraying ink, and a measurement unit 40 for measuring characteristics of a thin film formed of the sprayed ink. The transfer unit 30 may be configured to move the nozzle unit 20 along a predetermined path (for example, in the form of a “D” shape, etc.), and the transfer unit 30 may be formed between the nozzle unit 20 and the substrate. The nozzle unit 20 may be moved so that the spacing is adjusted, and the spraying distance may be adjusted according to the spacing.

In addition, in this document, the term "injection pattern distance" refers to the first It means the width of the conveying line ("-") to the second conveying line ("-"), and the adjustment of the spray pattern means the adjustment of the width. In addition, if the spray pattern distance is too wide, a void may occur between the thin films, and if the spray pattern distance is too short, a coffee ring effect may occur and a spot pattern may occur. At this time, the meaning of adjusting the "spray pattern distance" means that the applied layer is transferred while being transferred along the first transfer line ("ㅡ") and the coated layer applied while being transferred along the second transfer line ("ㅡ"). However, it means that the overlapping area is adjusted so that it is minimized.

In addition, the measuring unit 40 is provided to measure the properties of the coating thin film, for example, the area, thickness, surface roughness and uniformity of the coating thin film, and may be configured through a known sensor used in the coating process. The measuring unit 40 is provided to measure the properties of the coating thin film in real time in the coating process of the coating thin film.

The control unit 50 is provided to control the nozzle unit 20 and the transfer unit 30 based on the measured result of the measurement unit 40. In this document,

The control unit 50 first compares the thin film area and a predetermined area range (target area range), and secondly compares the thin film thickness and a predetermined thickness range (target thickness range), and the surface roughness and a predetermined roughness range (target area range) of the thin film. The roughness range) is compared in a third order, and the thickness uniformity of the thin film and a predetermined uniformity range (target uniformity range) are compared in a fourth order. That is, the control unit 50 is provided to sequentially compare whether the thin film area, the thin film thickness, the surface roughness, and the thickness uniformity are within a predetermined range.

Specifically, when the measured thin film area is out of a predetermined area range, the control unit 50 adjusts the spray distance, and when the measured thin film area is within a predetermined area range, the control unit 50 compares whether the measured thin film thickness is within a predetermined thickness range. And, when the measured thickness of the thin film is out of a predetermined thickness range, it is provided to control the ink injection amount.

On the other hand, by adjusting the spraying distance, as the spraying distance increases, a thin film coating is formed on a wider area, and as the spraying distance decreases, the spraying angle decreases, so that the spraying area decreases.

In addition, controlling the ink injection amount means controlling the amount of VO2 powder contained in the ink. Therefore, in the case of a thin film having a small amount of VO2 particles (a thin film coated with a low ink injection amount), the light sintering effect cannot be fully obtained, and further, optical/mechanical properties cannot be obtained.

In one embodiment, when the thin film area has a value smaller than the predetermined area range, the spraying distance may be increased, and when the thin film area has a value larger than the predetermined area range, the spraying distance may be reduced.

In addition, when the thin film thickness has a value smaller than the predetermined thickness range, the ink ejection amount can be increased, and when the thin film thickness has a value larger than the predetermined thickness range, the ejection amount can be reduced.

In addition, when the measured thin film thickness is within a predetermined thickness range, the control unit 50 compares whether the measured surface roughness of the thin film is within a predetermined roughness range, and when the surface roughness of the thin film is outside the predetermined roughness range, the deflector flow rate It can be provided to adjust. When the deflector flow decreases, the ink sprayed from the ultrasonic nozzle is coated on the substrate with a relatively large amount of solvent remaining. On the contrary, when the deflector flow rate increases, a part of the solvent evaporates while spraying from the ultrasonic nozzle to the substrate, resulting in particles other than ink. It is coated in a state close to. Accordingly, the surface roughness of the thin film is increased, and accordingly, the surface roughness of the thin film can be adjusted by adjusting the deflector flow rate.

In one embodiment, when the surface roughness of the thin film has a value greater than a predetermined roughness range, the deflector flow rate may be reduced. As the deflector flow rate decreases, the ink sprayed from the ultrasonic nozzle is coated on the substrate with a relatively large amount of solvent remaining, and when the solvent is maintained, the thin film roughness is improved by leveling.

In addition, after the deflector flow rate is adjusted, when the measured thin film area is out of a predetermined area range, the control unit 50 adjusts the spray distance, and when the thin film area is within a predetermined area range, the measured thin film thickness is predetermined. It may be provided to compare whether it is within the thickness range. That is, when the surface roughness is adjusted within the predetermined roughness range, the control unit 50 again compares whether the thin film area is within the predetermined area range. If the surface roughness of the thin film is adjusted within the predetermined roughness range, it may also be the case that the coating is concentrated in a partial area of the substrate, and therefore, it is possible to return to the thin film area comparison step to confirm that the coating is intact. have

In addition, after the ink injection amount is adjusted, when the measured thin film area is out of a predetermined area range, the control unit 50 adjusts the injection distance, and when the thin film area is within a predetermined area range, the measured thin film thickness is predetermined. It may be provided to compare whether it is within the thickness range. That is, when the thin film thickness is adjusted within the predetermined thickness range, the control unit 50 again compares whether the thin film area is within the predetermined area range.

In addition, when the measured surface roughness of the thin film is within a predetermined range, the control unit 50 compares whether the measured thickness uniformity of the thin film is within a predetermined uniformity range, and when the measured thickness uniformity of the thin film is outside the predetermined uniformity range. , It may be provided to adjust the spray pattern distance.

In one embodiment, when the thin film thickness uniformity has a value greater than a predetermined uniformity range, the spray pattern distance may be adjusted. The thin film thickness uniformity having a value greater than the predetermined uniformity range means that the thin film thickness is non-uniform. This may occur when the spray pattern distance is too narrow or too wide. If the spray pattern distance is too narrow, the above-described spot pattern remains, and when the uniformity is measured, the thickness deviation of the thin film increases and the thickness uniformity has a high value.If the spray pattern distance is too narrow, the thickness deviation increases as the coating is not intact, and the surface uniformity is high. Will have.

Referring to FIG. 2, a method of manufacturing an optical laminate (hereinafter referred to as a manufacturing method) using a coating device having the above structure will be described.

A method of manufacturing an optical layered product according to an embodiment of the present invention is a method of manufacturing an optical layered product using the coating device 1, wherein an ink containing vanadium oxide particles is applied on a substrate to obtain a predetermined thin film area, And forming a coating layer having a thin film thickness, surface roughness, and thickness uniformity.

At this time, in the manufacturing method, in the step of forming the coating layer, it is compared whether the measured thin film area is within a predetermined area range (S101), and when the measured thin film area is out of the predetermined area range, the spray distance is adjusted (S105). And, when the measured thin film area is within the predetermined area range, it is compared whether the measured thin film thickness is within the predetermined thickness range (S102), and when the measured thin film thickness is out of the predetermined thickness range, the ink injection amount is adjusted (S106). It includes the step of.

In addition, in the manufacturing method, in the step of forming the coating layer, when the measured thickness of the thin film is within a predetermined thickness range, a comparison is made to see if the surface roughness of the measured thin film is within a predetermined roughness range (S103), and the surface roughness of the thin film is predetermined. When out of the roughness range, including the step of adjusting the deflector flow rate (S107).

In addition, in the manufacturing method, in the step of forming the coating layer, when the surface roughness of the measured thin film is within a predetermined range, the thickness uniformity of the measured thin film is compared (S104), and the measured thickness of the thin film is within a predetermined uniformity range. When the uniformity is out of the predetermined uniformity range, adjusting the spray pattern distance (S108).

In addition, the manufacturing method includes a photoevaporation step of irradiating light to the coating layer to remove organic matter from the coating layer, and vanadium oxide particles included in the coating layer by irradiating light to photo-sinter vanadium oxide. It may include a photosintering step of manufacturing a thermochromic layer including clusters.

The manufacturing method using the light evaporation step and the light sintering step may be an effective method, in particular, when it is desired to form a thermochromic layer on a substrate made of a material sensitive to heat such as a polymer film. In the above manufacturing method, by irradiating light in two steps (photoevaporation step and light sintering step), a thermochromic layer having controlled visible light transmittance and infrared transmission/blocking properties is formed on the base material without causing physical deformation of the base material. Can be formed.

In the light evaporation step, most of the organic matter is removed by light irradiation, and in the light sintering step, vanadium oxide clusters are formed as bonds between vanadium oxide particles occur (neck growth) by light irradiation.

On the other hand, high-temperature heat is involved in the steps of photoevaporation and photo-sintering. Therefore, when the substrate is composed of a heat-sensitive material such as a polymer film, specific conditions of the photoevaporation and photo-sintering steps, for example, the type of light, the applied voltage (output voltage), the pulse width, and the number of pulses (repetitive irradiation of light) The number of times) and pulse interval (frequency) can be controlled to prepare a thermochromic layer having desired physical properties without physical deformation of the polymer film. For example, the light may be white light applied from the xenon lamp, the voltage may be 1000 to 3000V, the number of pulses may be 1 to 500 times, the pulse interval may be 1 to 10 Hz, the pulse width may be 1 ms to 10 ms.

First, in the photoevaporation step, as the number of pulses increases, the total energy increases to effectively remove the solvent. However, if the number of pulses is too high, the total energy increases, thereby causing physical deformation of the polymer film. The total energy is determined by the output voltage, pulse width, pulse interval, and number of pulses. The number of pulses may be appropriate, for example, 200 to 400 times, 250 to 350 times, or about 300 times.

As the pulse interval decreases, the processing time may decrease due to an increase in average power applied per second. The average power is determined by the output voltage, pulse width, and pulse interval. However, evaporation of the solvent may occur from a pulse interval of 1 Hz or more, and if the pulse interval is less than 1 Hz, the bed temperature may rise rapidly, thereby causing physical deformation of the polymer film.

In addition, as the output voltage increases, organic matters are effectively removed, but physical deformation of the polymer film may occur, and an appropriate voltage at which physical deformation does not occur may be in the range of 1000V to 1500V, 1100V to 1400V, or 1200V to 1300V.

In addition, as the output voltage increases, the concentration of organic matter (carbon or nitrogen) at the contact surface formed between the thermochromic layer and the substrate decreases.For example, the concentration of organic matter rapidly decreases at 1200V, and the initial organic matter removal occurs at 1100V.

On the other hand, the output voltage is related to the visible light transmittance and infrared transmittance of the laminate, and as the voltage increases, the polymer film physically deforms, resulting in a decrease in the visible light transmittance, and the infrared transmittance increases to a low voltage, e.g., 1200 V. However, at 1400V or higher, it falls due to the formation of cracks in the thermochromic layer.

The light sintering step is a step of transforming a specific light irradiation condition from the light evaporation step to a light sintering condition to be described later, and thus, the light evaporation step and the light sintering step may be performed continuously.

The output voltage of light in the photo-sintering step may be higher than the output voltage of light in the photoevaporation step. In the photosintering step, the output voltage of light should be selected within a range in which the vanadium oxide particles are sintered and the substrate is not deformed, for example, 1500V to 3000V, 1600 to 2500V, 1700V to 1800V, or about 1700V. I can.

In addition, the light evaporation step and the light sintering step are repeatedly irradiated with light having a constant pulse width, but the number of repeated light irradiation in the light sintering step may be less than or equal to the number of repetitions of light in the light evaporation step. In the photosintering step, as the number of irradiation increases, the spacing between the vanadium oxide particles narrows, so that vanadium oxide clusters may be formed. In the light sintering step, as the number of irradiations increases, the visible light transmittance and the infrared transmittance are improved, but when the number of times of irradiation is increased, the substrate is deformed and decreased. For example, infrared transmittance is improved up to 200 times, and visible light transmittance and infrared transmittance are deteriorated at 250 times or more. Therefore, the number of irradiation times in the photosintering step may be appropriate 50 to 300 times, 100 to 250 times, 150 to 200 times, or about 200 times.

In addition, the pulse width of light in the photo-sintering step may be smaller than the pulse width of light in the photoevaporation step. For example, in the photoevaporation step, the pulse width may be 1 to 10 ms, 2 to 8 ms, or 3 to 5 ms, and in the photo sintering step, the pulse width may be 0.1 to 5 ms, 0.5 to 3 ms, or 1 to 2 ms.

In one example, the light evaporation step and the light sintering step may be performed under an atmospheric atmosphere. In particular, the atmosphere in the photoevaporation step is related to the removal of organic matter, and, for example, the oxygen concentration in the bed acts as a major factor in the removal of organic matter. In particular, when proceeding in an inert atmosphere such as nitrogen or argon or in a vacuum atmosphere, most of the organic matter is not removed, so that the concentration of the organic matter on the surface increases. The concentration of organic matter on the surface is related to the infrared transmittance, for example, the concentration of organic matter on the surface increases in the order of atmospheric atmosphere, inert atmosphere, and vacuum atmosphere, and infrared transmittance decreases in the order of atmospheric atmosphere, inert atmosphere, and vacuum atmosphere. .

Preferred embodiments of the present invention described above are disclosed for the purpose of illustration, and those skilled in the art having ordinary knowledge of the present invention will be able to make various modifications, changes, and additions within the spirit and scope of the present invention. And additions should be seen as falling within the scope of the following claims.

1: coating device
10: ink supply
20: nozzle part
30: transfer unit
40: measuring unit
50: control unit

Claims (9)

A nozzle unit including an ink ejection unit and a deflector receiving ink from the ink supply unit;
A transfer unit for moving the nozzle unit during ink injection;
A measuring unit for measuring characteristics of a thin film formed of the jetted ink; And
Based on the measured result of the measurement unit, it includes a control unit for controlling the nozzle unit and the transfer unit,
When the measured thin film area is out of a predetermined area range, the control unit adjusts the spray distance, and when the measured thin film area is within a predetermined area range, the control unit compares whether the measured thin film thickness is within a predetermined thickness range, and the measured thin film When the thickness is out of the predetermined thickness range, a coating device provided to control the ink injection amount. The method of claim 1,
The control unit compares whether or not the measured surface roughness of the thin film is within a predetermined roughness range when the measured thickness of the thin film is within a predetermined thickness range, and when the surface roughness of the thin film is out of the predetermined roughness range, the coating provided to adjust the deflector flow rate Device. The method of claim 2,
After the deflector flow rate is adjusted, when the measured thin film area is out of a predetermined area range, the control unit adjusts the spray distance, and when the thin film area is within a predetermined area range, the measured thin film thickness is within a predetermined thickness range. Coating device prepared to be. The method of claim 1,
After the ink injection amount is adjusted, the control unit adjusts the injection distance when the measured thin film area is out of a predetermined area range, and compares whether the measured thin film thickness is within a predetermined thickness range when the thin film area is within a predetermined area range. Coating device prepared to be. The method of claim 2,
When the measured surface roughness of the thin film is within a predetermined range, the control unit compares whether the measured thickness uniformity of the thin film is within a predetermined uniformity range, and when the measured thickness uniformity of the thin film is outside the predetermined uniformity range, the spray pattern distance is determined. Coating device provided to adjust. As a method of manufacturing an optical laminate using the coating device according to claim 1,
Comprising the step of forming a coating layer having a predetermined thin film area, thin film thickness, surface roughness, and thickness uniformity by applying an ink containing vanadium oxide particles on a substrate,
In the step of forming the coating layer, when the measured thin film area is out of the predetermined area range, the spraying distance is adjusted, and when the measured thin film area is within the predetermined area range, the measured thin film thickness is within the predetermined thickness range. And, when the measured thickness of the thin film is out of the predetermined thickness range, the method of manufacturing an optical laminate comprising the step of adjusting the ink injection amount. The method of claim 6,
In the step of forming the coating layer, when the measured thickness of the thin film is within a predetermined thickness range, it is compared whether the surface roughness of the measured thin film is within a predetermined roughness range, and when the surface roughness of the thin film is out of the predetermined roughness range, the deflector flow rate Method of manufacturing an optical laminate comprising the step of controlling. The method of claim 7,
In the step of forming the coating layer, when the surface roughness of the measured thin film is within a predetermined range, it is compared whether the measured thickness uniformity of the thin film is within a predetermined uniformity range, and when the measured thickness uniformity of the thin film is out of the predetermined uniformity range. , A method of manufacturing an optical laminate comprising the step of adjusting the spray pattern distance. The method of claim 6,
A photoevaporation step of removing organic substances in the coating layer by irradiating light to the coating layer in a state in which coating is completed; And
A method of manufacturing an optical laminate, further comprising a photo-sintering step of producing a thermochromic layer including vanadium oxide clusters by irradiating light to photosinter vanadium oxide particles included in the coating layer.

Images