KR20160067268A - Method for coating multi-layer thin film - Google Patents

Method for coating multi-layer thin film Download PDF

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Publication number
KR20160067268A
KR20160067268A KR1020140172113A KR20140172113A KR20160067268A KR 20160067268 A KR20160067268 A KR 20160067268A KR 1020140172113 A KR1020140172113 A KR 1020140172113A KR 20140172113 A KR20140172113 A KR 20140172113A KR 20160067268 A KR20160067268 A KR 20160067268A
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South Korea
Prior art keywords
water
coating layer
coating
repellent
coating material
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KR1020140172113A
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Korean (ko)
Inventor
박성준
심진용
김현중
김홍철
김정래
임은주
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현대자동차주식회사
주식회사 쎄코
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Priority to KR1020140172113A priority Critical patent/KR20160067268A/en
Publication of KR20160067268A publication Critical patent/KR20160067268A/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention relates to a method to coat a multi-layer thin film allowing a multi-layer thin film with simultaneously improved light transmittance, water repellent ability, and weather resistance to be coated on a surface of a camera lens of a vehicle using a vacuum deposition method. According to an embodiment of the present invention, the method of coating the multi-layer thin film comprises: a preparation step of designing a low-reflective coating material considering light transmittance and adhesion; a pre-treatment step of adding an ultraviolet stabilizer to a water repellent coating material to increase weather resistance; and a coating step of positioning a base material in the chamber of a vacuum deposition device, and forming a low-reflective coating layer and a water repellent coating layer by depositing the low-reflective coating material and the water repellent coating material in order.

Description

[0001] METHOD FOR COATING MULTI-LAYER THIN FILM [0002]

The present invention relates to a multilayer thin film coating method, and more particularly, to a multilayer thin film coating method capable of coating a multilayer thin film having improved light transmittance, water repellency and weather resistance simultaneously on the surface of a camera lens of an automobile using a vacuum deposition method will be.

In general, the water-repellent coating technology which lowers the surface energy of a material is actively applied in various fields including automobile interior and exterior glass surfaces due to improvement of visibility, prevention of fingerprints, and antifouling effect.

For example, although recent applications for vehicle rear-view camera lenses and around-view monitoring for car parking assist systems have been increasing, problems such as contamination of camera lenses due to rain, dust, .

On the other hand, anti-reflection (AR) coating is applied to the camera lens to secure a high transmittance.

However, since the AR coating is usually deposited as an oxide, the contamination on the surface is severe, the contaminants are difficult to remove due to the high surface energy, and in the case of the contaminant coating material sold on the market for the purpose of contamination, the water repellent coating (water contact angle of about 100 degrees) It is difficult to maintain the water repellency and water repellency, and the durability thereof is deteriorated.

In general, a water-repellent coating is a technique of applying a low surface energy to a surface of a material so that the contact angle between water and the surface is 90 ° or more. In addition to the water-repellent performance, Therefore, the development of technology has been actively pursued.

Conventionally, as a technique for obtaining such low surface energy, a thin film utilizing fluoropolymers has been mainly used.

Fluoropolymers have high chemical and thermal stability, water repellency and oil-repellent properties, but they are pointed out as a disadvantage due to low resistance to organic solvents and lack of durability, especially lack of weatherbility.

For example, in the case of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), and perfluoroalkyl vinyl ether copolymer (PFA) But it is limited in application due to the resistivity to the organic solvent and the low adhesion to the substrate.

Among the fluorine polymers, polyvinyl fluoride (PVF) is used as a building glass due to high weatherability of the material, but it is pointed out that a low organic solvent resistance and fluidity are disadvantageous.

In recent years, techniques for surface treatment that imparts weather resistance, stain resistance, and high durability by lowering the surface energy of glass for exterior use in automobiles and buildings have been actively studied.

Conventionally, as the application of a camera to automobiles has increased, user's inconveniences such as contamination of a camera lens due to muddy water, dust, and the like have been continuously generated, so that a high- Anti-reflection (AR) coating.

The AR thin film coating is designed considering the refractive index of oxides such as MgF 2 , SiO 2 , TiO 2 and Al 2 O 3. MgF 2 is coated on the surface layer, Or by applying a general water repellent after other oxide deposition to impart stain resistance.

However, in these cases, the water repellency is not high (contact angle 90 to 100 °), and the formation of foreign matter and foreign matter can not be removed. As a result of the repulsive force between MgF 2 applied to the surface layer and the fluoropolymer, And the water repellent angle was deteriorated due to the separation of the coating layer.

Also, the Xeon accelerated test condition showed that the contact angle was less than 90 ° at the level of 600 kJ / m 2 .

Accordingly, there is a need to develop a technique capable of improving the water permeability of the lens with excellent water repellency and antifouling performance.

In order to solve the above problems, the present invention provides a multilayer thin film coating method capable of simultaneously improving light transmittance, water repellency and weatherability of a coating layer.

Further, a multilayer thin film coating method capable of improving the adhesion of the water repellent coating layer is provided.

According to an embodiment of the present invention, a multi-layer thin film coating method includes: preparing a low reflection coating material in consideration of a light transmittance and an adhesive force, thereby preparing the low reflection coating material and the water repellent coating material; A pretreatment step of adding an ultraviolet stabilizer to the water-repellent coating material so as to improve weatherability; And a coating step of positioning the base material in the chamber of the vacuum evaporation apparatus and sequentially depositing the low reflective coating material and the water repellent coating material to form a low reflective coating layer and a water repellent coating layer.

The low reflection coating layer may have a multi-layer structure in which a plurality of coating layers having different materials are stacked, and the coating layer to which the water-repellent coating layer is attached may be formed of SiO 2 .

The low reflection coating layer is formed by laminating 3 to 10 coating layers, and preferably has a thickness of 50 to 500 nm.

The water-repellent coating layer may include a fluorine polymer.

The ultraviolet stabilizer is preferably HALS (Hindered Amine Light Stabilizer).

The ultraviolet light stabilizer may be added in an amount of 1 to 10 wt% of the water-repellent coating material.

The water-repellent coating layer is formed to a thickness of 10 to 200 nm, and the contact angle thereof is preferably 100 to 150 °.

According to the embodiment of the present invention, the water repellent coating layer is laminated on the surface of the low reflection coating layer to improve the water repellency and weather resistance while improving the light transmittance by stacking the oxides having different refractive indexes in multiple layers to form the low reflection coating layer There is an effect.

In addition, there is an effect that the adhesion between the base material and the coating layer and the adhesion of the water-repellent coating layer are improved to improve the durability and life of the coating layer.

1 is a view showing a coating layer coated by a multilayer thin film coating method according to an embodiment of the present invention,
FIG. 2 is a diagram comparing the transmittance of a lens coated with a conventional water-repellent coating and a lens coated with a multilayer thin film coating method according to an embodiment of the present invention,
3 is a view showing the contact angle and weather resistance test results of the water-repellent coating layer formed using a vacuum deposition apparatus,
4 is a graph showing the contact angle and weatherability test results of the water-repellent coating layer to which the UV stabilizer is added,
5 is a view comparing images of a lens to which a low reflection coating layer is applied and a lens to which a multilayer thin film coating layer according to an embodiment of the present invention is applied.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments. For reference, the same numbers in this description refer to substantially the same elements and can be described with reference to the contents described in the other drawings under these rules, and the contents which are judged to be obvious to the person skilled in the art or repeated can be omitted.

1 is a view showing a coating layer coated by a multilayer thin film coating method according to an embodiment of the present invention.

As shown in FIG. 1, the multi-layer thin film coating method according to an embodiment of the present invention includes steps of preparing a low reflection coating material and a water repellent coating material, a pretreatment step of adding a UV stabilizer to a water repellent coating material provided and a vacuum deposition apparatus And a coating step of depositing a low reflection coating material and a water repellent coating material.

In the preparation step, the components of the low reflection coating material are designed in consideration of the adhesion between the water repellent coating material and the low reflection coating material, the light transmittance, and the like, and the low reflection coating layer 100) is designed, and a low-reflection coating material and a water-repellent coating material are prepared according to the designed components and the number of layers.

When the preparation step is completed, a water-repellent coating material is modified by adding an ultraviolet stabilizer or the like to the water-repellent coating material so as to improve the weatherability and the like of the water-repellent coating layer 200 as a surface of the coating layer in the pretreatment step.

When the water repellent coating material and the low reflection coating material are prepared, the base material 10 is placed in the chamber of the vacuum deposition apparatus in the coating step, and the low reflection coating material and the water repellent coating material are sequentially deposited to form the low reflection coating layer 100 and the water- (200).

The water-repellent coating layer 200 is formed of a fluorine polymer. In the present invention, a water-repellent coating material in which a fluorine polymer, graphite, and stainless steel are mixed is used. However, polytetrafluoroethylene (PTFE) (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkyl vinyl ether copolymer (PFA), and polyvinyl fluoride (PVF).

On the other hand, the low reflection coating layer 100 is formed in a multi-layered structure having a thickness of 50 to 500 nm in which 3 to 10 coating layers having different materials are laminated, and a coating layer contacting with the water repellent coating layer 200 is formed of a SiO 2 coating layer .

Accordingly, when coating a lens or the like, it is possible to improve light transmittance by coating oxides having different refractive indexes in multiple layers, and to improve the adhesive strength of the water-repellent coating layer 200, thereby improving the lifetime of the water-repellent coating layer 200 have.

2 is a view comparing the transmittance of a lens (a) to which a conventional water-repellent coating is applied and a lens (b) coated with a multilayer thin film coating method according to an embodiment of the present invention.

As shown in FIG. 2, in the case of a lens to which a water-repellent coating is applied, since the MgF 2 layer of the low-reflection coating layer to which the water-repellent coating layer is attached has a repulsive force with the fluoropolymer among the components of the water-repellent coating material, I had a separate issue.

On the other hand, the low reflection coating layer 100 formed according to the embodiment of the present invention is designed such that the low reflection coating layer 100 is formed by coating different oxides such as SiO 2 and TiO 2 , and the coating layer contacting the water repellent coating layer 200 SiO 2 coating layer, it was found that the transmittance was improved by 1.2% while improving the adhesion with the water-repellent coating layer 200 to improve the lifetime of the coating layer.

FIG. 3 is a view showing contact angle and weatherability test results of a water-repellent coating layer formed using a vacuum deposition apparatus, and FIG. 4 is a view showing contact angle and weatherability test results of a water-repellent coating layer to which a UV stabilizer is added.

3, a low reflection coating material and a water-repellent coating material are designed according to an embodiment of the present invention. That is, when the water-repellent coating material is coated without adding a UV stabilizer, The SiO 2 / TiO 2 / SiO 2 coating layer, which was developed for securing a high transmittance, was coated through a vacuum deposition process. When a water repellent coating layer 200 was formed by mixing a fluorine polymer, graphite, stainless steel, (120 °) higher than the contact angle (90 to 110 °) of the conventional water-repellent coating layer 200, which is an average of 116.1 °.

However, although the contact angle is maintained up to 300 kJ / ㎡, the contact angle is decreased when irradiated at 500 kJ / ㎡ or more, and the water repellency is almost lost when irradiated at 600 kJ / ㎡.

This is because the chemical bonding between the fluorine polymer and the carbon of the water repellent coating layer 200 is broken by the subsequent ultraviolet ray exposure.

On the other hand, it is preferable that the water-repellent coating layer 200 is formed to a thickness of 10 to 200 nm because if it is less than 10 nm, it is difficult to improve the weatherability, and if it exceeds 200 nm, the light transmittance may decrease.

4, the low reflection coating layer 100 is formed by coating a SiO 2 / TiO 2 / SiO 2 coating layer, which has been developed for securing a low reflection / high transmittance, through a vacuum deposition process, and a fluoropolymer, a graphite, When the water-repellent coating layer 200 is formed by adding 3 wt% of a Hindered Amine Light Stabilizer (HALS) based on stainless steel in addition to stainless steel, a high contact angle of 102.3 ° is maintained even when irradiated with ultraviolet rays of 600 kJ / m 2.

This is because the HALS-based ultraviolet blocking agent added to the water-repellent material removes the free radicals generated during the photolysis reaction, thereby suppressing the destruction of the chemical bond due to ultraviolet rays.

Therefore, it can be seen that the weather resistance of the water-repellent coating layer 200 is improved by adding an ultraviolet stabilizer to the water-repellent coating material, and adding an ultraviolet stabilizer to 1 to 10 wt% of the water-repellent coating material.

In addition, it is preferable to use HALS as an ultraviolet stabilizer because HALS has a tetra-methyl piperidine structure as a ultraviolet stabilizer that simultaneously satisfies both peroxide release and radical scavenger functions, but its main function is to remove free radicals This is because it can serve as a radical scavenger for stopping the reaction.

Also, unlike ultraviolet absorbers, HALS is excellent in surface protection and can be applied to products having a thin cross section, and it does not affect the light transmittance because it does not impart coloring unlike a quencher.

5 is a view comparing images of a lens a to which a low reflection coating layer is applied and a lens to which a multilayer thin film coating layer b according to an embodiment of the present invention is applied.

As shown in FIG. 5, the water repellent coating layer 200 is not formed and SiO 2 / TiO 2 / SiO 2 When the low reflection coating layer 100 in which the coating layers are sequentially laminated is formed through the vacuum deposition process, the water repellent coating layer 200 is laminated on the low reflection coating layer 100 It can be seen that the distorted shape does not appear when the water droplet is formed.

As described above, according to the embodiment of the present invention, the light transmittance is improved by forming the low reflection coating layer 100 by stacking the oxides having different refractive indexes in multiple layers, and the water repellent coating layer 200 ), It is possible to improve water repellency and antifouling property, ensure visibility in rainy weather, and improve weather resistance.

Although the present invention has been described with reference to the preferred embodiments thereof, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined in the following claims. It can be understood that

10: Base material 100: Low reflection coating layer
200: Water repellent coating layer

Claims (7)

Preparing a low reflective coating material in consideration of light transmittance and adhesive force, and thereby preparing the low reflective coating material and the water repellent coating material;
A pretreatment step of adding an ultraviolet stabilizer to the water-repellent coating material so as to improve weatherability; And
And a coating step of forming a low reflection coating layer and a water-repellent coating layer by sequentially depositing the low reflection coating material and the water-repellent coating material by placing the base material in a chamber of the vacuum evaporation apparatus.
The method according to claim 1,
The water-repellent coating layer includes a fluorine polymer, and the low reflection coating layer each other doedoe composed of a plurality of coating layers are stacked multi-layer structure having different material and the coating layer on which the water repellent coating layer attachment, characterized in that formed of SiO 2, a multi-layer Thin film coating method.
The method of claim 2,
The low reflection coating layer may be formed,
Wherein the coating layer is composed of 3 to 10 coating layers, and the thickness of the coating layer is 50 to 500 nm.
The method according to claim 1,
The ultraviolet stabilizer,
HALS (Hindered Amine Light Stabilizer).
The method of claim 4,
The ultraviolet stabilizer,
Wherein the water-repellent coating material is added in an amount of 1 to 10 wt% of the water-repellent coating material.
The method according to claim 1,
The water-
Wherein the coating layer is formed to a thickness of 10 to 200 nm.
The method according to claim 1,
Wherein the water-repellent coating layer has a contact angle of 100 to 150 °.
KR1020140172113A 2014-12-03 2014-12-03 Method for coating multi-layer thin film KR20160067268A (en)

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