KR20170065367A - A high water-repellent coating thin film having improved adhesive strength - Google Patents
A high water-repellent coating thin film having improved adhesive strength Download PDFInfo
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- KR20170065367A KR20170065367A KR1020150171710A KR20150171710A KR20170065367A KR 20170065367 A KR20170065367 A KR 20170065367A KR 1020150171710 A KR1020150171710 A KR 1020150171710A KR 20150171710 A KR20150171710 A KR 20150171710A KR 20170065367 A KR20170065367 A KR 20170065367A
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- silane
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
TECHNICAL FIELD The present invention relates to a thin film having super water-repellent properties, and is characterized in that adhesion to a base material such as a lens is improved. Specifically, the water-repellent layer is formed of an organic / inorganic composite material in which a silicon compound and a fluorine compound are combined to form a water repellent layer having high thermal, physical and chemical stability and super water repellency, and excellent durability and weather resistance of a fluorine compound Respectively. In addition, an adhesive layer is formed between the water repellent layer and the base material to reduce the interfacial stress between the two layers, thereby improving the adhesive strength and abrasion resistance between the water repellent coating film and the base material.
Description
TECHNICAL FIELD The present invention relates to a thin film having super water-repellent properties, and is characterized in that adhesion to a base material such as a lens is improved.
The water-repellent coating is a technique that imparts a low surface energy to a material so that the contact angle between the surface of the material and the water is 90 ° or more.
When water repellent coating is applied, water droplets do not form on the surface of the material due to high contact angle. Therefore, it is possible to improve the visibility of the material at the time of rainstorm, to prevent the occurrence of fingerprints, and to easily remove (stain-proof effect) when the contaminants are buried in the material.
Accordingly, water-repellent coating technology is important in various fields. Recently, with the development of Advanced Driver Assistance System (ADAS), there has been a great interest in the rear camera lens of the vehicle or the monitoring of the surround-view.
When water repellent coating is applied to the lens system of ADAS, it is possible to solve the problem that a malfunction occurs due to rain drops (raindrops), dust or muddy water in the rain, or the visibility deteriorates.
In the past, fluorine compounds (fluorine polymers) having high chemical and thermal stability and water-repellent properties were mainly selected for use as water-repellent coatings.
Korean Patent Laid-Open No. 10-2014-0122262 is a technical feature that various fluorine-containing copolymers are added to a coating agent to realize excellent oil repellency and / or water repellency.
However, fluorine compounds have a disadvantage of poor durability. Especially, it is reluctant to use it in industries where WEATHER-RESISTANT is so weak that it is necessary to consider harsh environments such as automobiles and interior and exterior materials of buildings.
Further, since the coating agent based on the fluorine compound has low adhesion to the surface of a lens or the like made of an organic polymer material, it may cause problems such as peeling. That is, there is a limit in that the wear resistance is poor and the service life is short.
Therefore, development of a super water-repellent coating film which does not lose its water repellency and oil repellency even in a harsh environment due to weatherability and abrasion resistance is desperately needed.
SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and has the following objectives.
An object of the present invention is to provide a coating film excellent in weatherability and abrasion resistance and having super water repellency.
It is another object of the present invention to provide a coating film having a super water-repellent property with improved adhesion to a base material such as a lens.
The object of the present invention is not limited to the above-mentioned object. The objects of the present invention will become more apparent from the following description, which will be realized by means of the appended claims and their combinations.
In order to achieve the above object, the present invention can include the following configuration.
The super-water-repellent coating film having improved adhesion according to the present invention may include a water-repellent layer made of an organic / inorganic composite material in which a silicon compound and a fluorine compound are combined, and an adhesive layer formed between the base material and the water-repellent layer.
In the super-water-repellent coating film having improved adhesion according to the present invention, the silicon compound may be at least one selected from the group consisting of octadecyltrimethoxy silane, octyltrimethoxy silane, methyltrimethoxy silane, Ethyltrimethoxy silane, ethyltriethoxy silane, propyltrimethoxy silane, n-propyltriethoxy silane, isopropyltriethoxy silane, isopropyltriethoxy silane, isopropyltriethoxysilane, n-butyltrimethoxy silane, isobutyltrimethoxy silane, phenyltrimethoxysilane, N- (2-aminoethyl) -3- ( Aminopropyltrimethoxy silane, 3-mercaptopropyltrimethoxy silane, 3-mercaptopropyltriethoxysilane (3-mercaptopropyltrimethoxysilane), and 3-mercaptopropyltrimethoxysilane. -mercaptop 3-aminopropyltrimethoxy silane, 3-aminopropyltrimethoxy silane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (aminopropyltrimethoxy silane) (meth) acryloxypropyltrimethoxy silane, 3- (meth) acryloxypropyltriethoxy silane, phenylaminopropyltrimethoxy silane, vinyltriethyloxy silane, Vinyltrimethoxy silane, and allyltrimethoxy silane, or a combination thereof.
In the ultra-water-repellent coating film having improved adhesion according to the present invention, the fluorine compound may be at least one selected from the group consisting of perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene , FEP) and perfluoroalkyl vinyl ether copolymers, or a combination thereof.
In the super-water-repellent coating film having improved adhesion according to the present invention, the fluorine content of the water-repellent layer may be 10 to 50 wt%.
In the super-water-repellent coating film having improved adhesion according to the present invention, the water-repellent layer may have a thickness of 10 to 200 nm.
In the super-water-repellent coating film having improved adhesion according to the present invention, the water-repellent layer may have a contact angle of 100 to 150 °.
In the super-water-repellent coating film having improved adhesion according to the present invention, the base material is a lens made of an organic polymer, and the adhesive layer may be composed of silicon oxide (SiO 2 ).
In the super-water-repellent coating thin film having improved adhesion according to the present invention, the adhesive layer may have a thickness of 10 to 100 nm.
The present invention includes the above-described configuration, and thus has the following effects.
The super-water-repellent coating film according to the present invention is excellent in water repellency and can prevent a device using the thin film from malfunctioning due to weather and dirt.
Further, the super-water-repellent coating film according to the present invention is excellent in weatherability, so that excellent water repellency can be maintained even when it is applied to harsh environments such as automobiles and buildings.
Also, since the super-water-repellent coating film according to the present invention has excellent adhesion to the surface of a lens or the like and is not easily peeled off, the water-repellent function can be exhibited stably for a long time.
The effects of the present invention are not limited to the effects mentioned above. It should be understood that the effects of the present invention include all reasonably possible effects in the following description.
1 is a cross-sectional view of a super water-repellent coating film according to the present invention.
Fig. 2 shows the contact angle of Comparative Example 1. Fig.
Fig. 3 shows the contact angle of Example 1. Fig.
4 is an SEM (Scanning Electron Microscope) image after the abrasion resistance test of Comparative Example 2. Fig.
5 is an SEM (Scanning Electron Microscope) image after the abrasion resistance test of Example 2. Fig.
Hereinafter, the present invention will be described in detail by way of examples. The embodiments of the present invention can be modified into various forms as long as the gist of the invention is not changed. However, the scope of the present invention is not limited to the following embodiments.
In the following description, well-known functions or constructions are not described in detail since they would obscure the invention. As used herein, " comprising "means that other elements may be included unless otherwise specified.
1 shows a base water-
The base material may be a lens or a substrate of an optical element used for a display device, a spectacle, an automobile, a building, and the like. But is not limited to, a lens used in an ADAS (Advanced Driver Assistance System) of an automobile.
However, the base material may be made of an organic polymer material as described later. Details will be described later.
The base material may have a constant shape such as a curved line and a plane, and is not limited to the shape of FIG. Also, since the super-water-repellent coating film is coated on the base material, it may have the same shape as the surface of the base material.
The super-water-
The water-
The water-repellent layer may be formed of an organic / inorganic composite material in which a silicon compound and a fluorine compound are combined.
The fluorine compound is low in resistance to an organic solvent and lacks in weather resistance, so that it is difficult to use the fluorine compound in an industrial field such as automobiles and construction which are in a harsh environment.
Accordingly, in the present invention, a silicone compound is bonded to a fluorine compound to form an organic / inorganic composite material, and a water repellent layer is formed using the composite.
Since the fluorine compound has a polar functional group, it is close to the silicon compound. Specifically, the organic / inorganic composite material may have a fluorine substituent on the main skeleton of the silicon material.
Accordingly, the water-repellent layer can have a high thermal, physical and chemical stability and super water repellency, and excellent durability and weatherability of an inorganic material (silicon compound) possessed by the fluorine compound.
For this purpose, it is important to appropriately blend the silicone compound and the fluorine compound. For this purpose, it is preferable that the water-repellent coating layer has a fluorine content of 10 to 50 wt%.
The silicone compound may be selected from the group consisting of octadecyltrimethoxy silane, octyltrimethoxy silane, methyltrimethoxy silane, ethyltrimethoxy silane, ethyltriethoxysilane but are not limited to, ethyltriethoxy silane, propyltrimethoxy silane, n-propyltriethoxy silane, isopropyltriethoxysilane, n-butyltrimethoxy silane, silane, isobutyltrimethoxy silane, phenyltrimethoxysilane, N- (2-aminoethyl) -3- (aminopropyltrimethoxysilane) (N- (2-aminoethyl) Aminopropyltrimethoxy silane, 3-mercaptopropyltrimethoxy silane, 3-mercaptopropyltriethoxy silane, 3-aminopropyltriethoxy silane, 3-aminopropyltrimethoxy silane, -aminopropyltr iethoxy silane, 3-aminopropyltrimethoxy silane, 3- (meth) acryloxypropyltrimethoxy silane, 3- (meth) acryloxypropyl tri (Meth) acryloxypropyltriethoxy silane, phenylaminopropyltrimethoxy silane, vinyltriethyloxy silane, vinyltrimethoxy silane, and allyltrimethoxysilane and allyltrimethoxy silane, or a combination thereof.
The fluorine compound may be selected from the group consisting of perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), and perfluoroalkyl vinyl copolymer ether copolymer, or a combination thereof.
The water-repellent layer may have a thickness of 10 to 200 nm. If it is less than 10 nm, it is difficult to expect improvement in weatherability. If it is more than 200 nm, the transmittance of the super water repellent coating film may be lowered.
The adhesive layer (22) is formed between the base material and the water-repellent layer to reduce the stress between the both layers. Therefore, the adhesion between the super-water-repellent coating film and the base material can be improved, which can directly lead to an improvement in wear resistance such as prevention of peeling of the super-water-repellent coating film.
Since the water-repellent layer contains a fluorine compound, the adhesion to a base material made of an organic polymer material is remarkably deteriorated. In the present invention, the adhesive layer is formed between the base material and the water-repellent layer to serve as a kind of buffer zone.
Accordingly, the adhesive layer may be preferably a silica oxide film composed of an organic polymer material (base material) and silicon oxide (SiO 2 ) that is close to the silicon compound of the water-repellent layer.
The adhesive layer may have a thickness of 10 to 100 nm. If the thickness is less than 10 nm, it is difficult to improve the adhesive strength. If the thickness is more than 100 nm, it may be difficult to form the adhesive layer by the dry deposition process, and the transmissivity of the super water repellent coating film may also be lowered.
The super-water-
Hereinafter, the present invention will be described in more detail with reference to experimental examples. However, these examples are for illustrating the present invention and the scope of the present invention is not limited thereto.
EXPERIMENTAL EXAMPLE 1 Measurement of Contact Angle of Water Repellent Layer
(Example 1) A super-water-repellent coating film according to the present invention was formed on the surface of a lens. Specifically, after forming an adhesive layer on the surface of the lens, the water-repellent layer was formed on the upper side of the adhesive layer. A dry vacuum deposition method was used as described above.
The water-repellent layer was formed of an organic / inorganic composite material in which PFPE and trimethoxysilane were combined. At this time, the fluorine content of the water-repellent layer was 15 wt%, and the thickness was adjusted to 20 nm or less.
The adhesive layer was formed of silicon oxide. At this time, the thickness of the adhesive layer was adjusted to 10 nm or more.
(Comparative Example 1) A lens not having the super-water-repellent coating film formed thereon was prepared.
The contact angles of Example 1 and Comparative Example 1 were measured. The results are shown in Figs. 2 and 3.
FIG. 2 shows the contact angle of Comparative Example 1, and FIG. 3 shows the contact angle of Example 1. FIG.
Referring to FIG. 2, when the super-water-repellent coating film is not formed, the contact angle with water is 60 to 80 °, which indicates a surface property close to hydrophilic.
On the other hand, referring to FIG. 3, it can be seen that when the super-water-repellent coating film according to the present invention is formed, the contact angle with water is 115 to 120 °, and the contact angle corresponding to super water repellency is measured.
Experimental Example 2 - Measurement of abrasion resistance with and without adhesive layer
(Example 2) A lens having the same super-water-repellent coating film as in Example 1 was prepared.
(Comparative Example 2) The same lens as that of Example 1 was prepared except that no adhesive layer was formed.
The abrasion resistance test was carried out for Example 2 and Comparative Example 2. The surface of the coating film was subjected to a reciprocating motion 1,500 times by applying a force of 9.8 N with an eraser, and then the degree of peeling and the contact angle of the coating film were measured. The results are shown in FIGS. 4 and 5. FIG.
Fig. 4 is an SEM image of the abrasion resistance test of Comparative Example 2, and Fig. 5 is an SEM image of the abrasion resistance test of Example 2. Fig.
The contact angle before the abrasion resistance test of Example 2 and Comparative Example 2 was measured at about 120 °.
After the abrasion resistance test, the contact angle of Comparative Example 2 was measured at about 65 °, and the contact angle of Example 2 was measured at about 108.4 °.
Also, referring to FIG. 4, it can be seen that a comparatively large amount of the coating film is peeled off due to the abrasion resistance test in the case of Comparative Example 2. On the other hand, referring to FIG. 5, it can be seen that, in Example 2, the roughness of the surface was somewhat changed, but the coating film was not peeled off as a whole.
That is, in Example 2, since the adhesive strength between the water-repellent layer and the base material was improved by the adhesive layer, the water-repellent layer was hardly peeled off even though the wear resistance test was performed.
The present invention has been described in detail. However, the scope of rights of the present invention is not limited thereto, but is defined by the following claims.
10: base metal
20: super water repellent coating thin film
21: Water repellent layer
22: Adhesive layer
Claims (8)
And an adhesive layer formed between the base material and the water-repellent layer.
The silicone compound may be selected from the group consisting of octadecyltrimethoxy silane, octyltrimethoxy silane, methyltrimethoxy silane, ethyltrimethoxy silane, ethyltriethoxysilane but are not limited to, ethyltriethoxy silane, propyltrimethoxy silane, n-propyltriethoxy silane, isopropyltriethoxysilane, n-butyltrimethoxy silane, silane, isobutyltrimethoxy silane, phenyltrimethoxysilane, N- (2-aminoethyl) -3- (aminopropyltrimethoxysilane) (N- (2-aminoethyl) Aminopropyltrimethoxy silane, 3-mercaptopropyltrimethoxy silane, 3-mercaptopropyltriethoxy silane, 3-aminopropyltriethoxy silane, 3-aminopropyltrimethoxy silane, -aminopropyltr iethoxy silane, 3-aminopropyltrimethoxy silane, 3- (meth) acryloxypropyltrimethoxy silane, 3- (meth) acryloxypropyl tri (Meth) acryloxypropyltriethoxy silane, phenylaminopropyltrimethoxy silane, vinyltriethyloxy silane, vinyltrimethoxy silane, and allyltrimethoxysilane (allyltrimethoxy silane) or a combination thereof.
The fluorine compound may be selected from the group consisting of perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), and perfluoroalkyl vinyl copolymer ether copolymer, or a combination thereof.
Wherein the water repellent layer has a fluorine content of 10 to 50 wt%.
Wherein the water-repellent layer has a thickness of 10 to 200 nm.
Wherein the water-repellent layer has a contact angle of 100 to 150 °.
The base material is a lens made of an organic polymer,
The adhesive layer is a silicon oxide (SiO 2) of adhesive a super water-repellent coating films improved.
Wherein the adhesive layer has a thickness of 10 to 100 nm.
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| KR1020150171710A KR20170065367A (en) | 2015-12-03 | 2015-12-03 | A high water-repellent coating thin film having improved adhesive strength |
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| KR1020150171710A KR20170065367A (en) | 2015-12-03 | 2015-12-03 | A high water-repellent coating thin film having improved adhesive strength |
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