CN113549872A - Black coating - Google Patents
Black coating Download PDFInfo
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- CN113549872A CN113549872A CN202110370178.5A CN202110370178A CN113549872A CN 113549872 A CN113549872 A CN 113549872A CN 202110370178 A CN202110370178 A CN 202110370178A CN 113549872 A CN113549872 A CN 113549872A
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- functional layer
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- coating
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- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 239000002346 layers by function Substances 0.000 claims abstract description 102
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 239000010410 layer Substances 0.000 claims abstract description 42
- 239000011241 protective layer Substances 0.000 claims description 20
- 230000007704 transition Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 229910020295 SiOyNz Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 229910004205 SiNX Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910010037 TiAlN Inorganic materials 0.000 description 1
- 229910008322 ZrN Inorganic materials 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/10—Glass or silica
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a substrate having a very dark or black coating comprising a substrate having a coating applied thereto, said coating comprising in order the following parallel layers: a first functional layer adjacent to the substrate, and a second functional layer, wherein the first functional layer has a dark appearance, and wherein the second functional layer has a thickness less than the wavelength of visible light. The invention also provides a method of making the coated substrate and a product comprising the coated substrate.
Description
Technical Field
The present invention relates to very dark or black coatings on substrates, to methods of making the coatings, and to methods of use.
Background
A number of deposition techniques are used to coat the substrate. Vapor deposition techniques are commonly used to form thin film deposited layers in a variety of applications, including microelectronics and applications on high-use frequency products. Such deposition techniques can be divided into two broad categories, the first category being known as Chemical Vapor Deposition (CVD), which generally refers to a deposition process that occurs as a result of a chemical reaction. Common CVD processes include semiconductor silicon layer deposition, epitaxy, and thermal oxidation.
The second type of deposition technique is commonly referred to as Physical Vapor Deposition (PVD). PVD generally refers to the deposition of solid matter resulting from physical reactions. The main concept of PVD processes is that the deposited material is transferred to the substrate surface by direct physical means. Generally, no chemical reaction occurs during the process, and the thickness of the deposited layer is independent of the kinetics of the chemical reaction.
Sputtering is a known PVD technique that deposits elements or compounds on a substrate, wherein atoms, ions or molecules are sputtered from a target material (also called a sputtering target) by particle bombardment, thereby causing the sputtered atoms or molecules to deposit as a thin film on the substrate surface.
Many consumer products require very dark or black coatings. Such coatings are known to contain carbon, for example some metal carbides, however not all materials can use a carbon containing coating. If some metals, including zinc, magnesium, aluminum, and alloys thereof, are combined with carbon, a battery effect may result, resulting in accelerated corrosion of the metal substrate. Thus, the surfaces of these materials cannot be coated with a carbon-containing coating, even though these materials are often used in some manufacturing industries and even preferably used in very dark colors.
However, the aesthetic requirements for very dark or black coatings are still large in the industry.
It is therefore an object of the present invention to provide very dark or black coatings, particularly for consumer products where the appearance of a very dark or black coating is desired. It is another object of particular examples to provide such coatings optimized to address and/or overcome one or more of the problems described above. The object of a particular example is to provide a very dark or black interference type coating.
Disclosure of Invention
Accordingly, the present invention provides a coated substrate comprising a substrate to which a coating is applied, the coating comprising in order the following base coats: a first functional layer adjacent to the substrate, and a second functional layer, wherein the first functional layer has a very dark appearance, and wherein the second functional layer has a thickness that is less than the wavelength of visible light.
Advantageously, the addition of the second functional layer makes the coating appear darker (darker) than the first functional layer. Optionally, a third transparent functional layer is provided to protect the coating.
The present invention also provides a method of providing a very dark or black coating on a substrate comprising successively depositing a first functional layer and a second functional layer of the coating of the present invention and, in the present case, a third layer and any further functional layers. A further functional layer may be located between the second and third functional layers. Further functional layers may be located on the third functional layer, for example a scratch-resistant layer and/or a non-reflective layer.
In addition, products comprising the coatings of the present invention are also provided. Examples of products include in particular moulded products, but also products made of materials which hitherto could not be easily coated with a carbon-containing coating, such as zinc, magnesium, aluminium and alloys thereof. Further provided are specific products, such as consumer medical devices, such as shavers and portions thereof that include the coatings of the present invention. In one particular product, razor handles are die cast from zinc and coated with a black coating of the present invention.
Detailed Description
The preferred first functional layer of the present invention is visually very dark or black. The first functional layer has specific L, a and b values to provide the coating with a very dark or black primary color.
Suitably, the first functional layer has an L value of 55 or less, preferably 50 or less, most preferably 48 or less.
Suitably, the values of a and b for the first functional layer are in the range 10 to-10, preferably 5 to-5, most preferably 2 to-2, respectively.
CIE Lab is the Commission on International illumination (CIE) and the corresponding standard ISO/CIE 11664-4: 2019 to define a well-known chromaticity space. According to the CIE Lab system, UV/Vi is usedsThe spectrophotometer measures the color. L, a and b values are typically measured according to CIE L a b (or CIE Lab) color space. For simplicity, the values of L, a, and b are referred to as L, a and b throughout the application. The value of L is usually between 0 and 100, where L-0 denotes perfect black and L-100 denotes diffuse reflectionWhite.
The "a" value represents a green red component, the more negative "a" value represents a larger green component, and the more positive "a" value represents a larger red component. The "b" value represents a blue yellow portion, the more negative value of b represents a larger blue portion, and the more positive value represents a larger yellow portion.
The spectrophotometer measures color under a standard light source, most commonly D65 sunlight. D65 is produced by standard ISO 11664-2: 2007 definition (this standard is the same around the world and is independent of local environment).
The first functional layer is typically black or visually black. According to the invention, the perception of the layer by the viewer is influenced by the second functional layer, making the overall combination appear darker. This usually requires, i.e. requires, the second functional layer, since the first functional layer is not black enough by itself.
The thickness of the first functional layer is generally not important, since the inherent properties of this layer are not significantly affected by its thickness. Optionally, the substrate is made entirely of the material of the first functional layer. However, it is typically deposited on a substrate and preferably does not significantly change the shape or size of the substrate, and may be an expensive or expensive to deposit material, which is typically relatively thin, e.g., 5 μm or less; the thickness thereof may suitably be from 0.2 μm to 1.8. mu.m, preferably from 0.4 μm to 1.5. mu.m, most preferably from 0.6 μm to 1.0. mu.m.
Suitable materials for the first functional layer are compounds such as metals or metal nitrides, for example silicon, aluminum or nitrides of some transition metals, for example titanium, zirconium, chromium, aluminum, niobium, hafnium and mixtures thereof. For example, the first functional layer may comprise or consist of Ti, Zr, ZrN, TiZrx, CrSiNx, TiAlN, CrAlN, TiNbN, TiCN, CrN, TiN, HfN, etc., where x is a variable. Preferably, x is between 1 and 5, most preferably x has a value of about 2.
In particular, a preferred embodiment of the invention has a first functional layer which is or comprises TiZrNx, as described below. Where x is an integer value, and the value of x may be different in different embodiments of the invention. However, in any given embodiment, the value of x in TiZrNx remains substantially constant. When the first function isThe layer comprises TiZrNxWhen x is 2, the preferred value is. A preferred value of x for the first functional layer is 2.
In other examples, the first functional layer is or includes CrN, TiN, ZrN, CrSiN. Thus, the first functional layer is a dark bottom layer of the coating.
The first functional layer may also serve as an underlayer to improve the bonding between the substrate and other layers of the invention, in particular the second functional layer.
The refractive index of the first functional layer may be between 1.1 and 3.0, preferably between 1.2 and 2.8, most preferably between 1.3 and 2.6.
The second functional layer is relatively thin to produce the effect of darkening the already dark colored first functional layer. The thickness of the second functional layer is therefore chosen in order to further deepen the overall appearance of the coating by interference.
The thickness of the second functional layer may be up to about 100 nm. Suitable thicknesses are in the range of from 30nm to 100nm, for example from 40nm to 60nm, preferably from 50nm to 60nm, most preferably from 15nm to 58 nm.
Thus, according to the present invention, a second functional layer is used which is relatively thin and has a different refractive index than the first functional layer, whereby the phase difference between light reflected from the upper surface of the first functional layer and light reflected from the upper surface of the second functional layer is about pi, resulting in destructive interference over a wide range or all wavelengths of light, the net effect being visual darkening of colour. Thus, a very dark and black coating can be obtained, as is the case in the following specific examples.
Preferably, the second functional layer is SiNx, ZrOx or TiOj, where x and j are variables. Preferred values of x for the second functional layer are typically between 1 and 2, e.g. 4/3. Preferred values of j for the second functional layer are generally between 1.5 and 2.5, preferably 2.
Preferably, the second functional layer is SiNx, where x is a variable. Preferred values of x for the second functional layer are typically between 1 and 2, e.g. 4/3.
A particularly preferred example of the invention shown below comprises a first functional layer which is or comprises TiZrNx and a second functional layer of SiNx. x is defined in each case as described above.
In the examples of the invention described in more detail below, the first functional layer has a higher refractive index than the second functional layer. When optional transition layers or protective layers are present, the second functional layer preferably has a lower refractive index than these transition/protective layers. Without being bound by theory, light reflected from the upper (outermost) surface of the first functional layer interferes with light reflected from the upper surface of the second functional layer to cancel; when light propagates from a medium with a lower refractive index to a medium with a higher refractive index, pi phase difference occurs in light reflected from an interface between the two media; in the present invention, light reflected into the coating from the interface between the first functional layer and the second functional layer undergoes a pi phase difference; in contrast, light reflected into the coating from the interface between the protective/transitional layer and the second functional layer is not out of phase.
The refractive index of the second functional layer may be between 1.0 and 3.0, preferably between 1.2 and 2.8, most preferably between 1.4 and 2.0.
The refractive index of the second functional layer may be between 1.5 and 3.0, preferably between 1.8 and 2.8, most preferably between 1.9 and 2.7.
The specific preferred examples of the present invention shown below include a protective layer.
The protective layer is preferably relatively transparent. The transparency of the layer is generally greater than 40%, preferably greater than 50%. One possible method of measuring clarity is described in ASTM D-1000.
The protective layer preferably has a low refractive index. The refractive index of this layer is preferably higher than the refractive index of the second functional layer and higher than the refractive index of the optional transition layer (if present).
Preferred materials for the protective layer include SiO2、TiO2SiNx and other materials with similar properties, wherein the preferred value of x for the second functional layer is typically between 1 and 2, e.g. 4/3.
Preferred materials for the protective layer include SiO2、TiO2And other materials with similar properties.
The refractive index of the protective layer is preferably between 1.3 and 3.0, preferably between 1.4 and 2.8, and most preferably between 1.4 and 2.7.
The thickness of the protective layer may be 1.0 μm to 2.5 μm, preferably 1.3 μm to 2.2 μm, most preferably 1.5 μm to 2.0 μm.
The coating may optionally include a transition layer. The transition layer may have a thickness of 0.5 μm to 2.0 μm, preferably 1.0 μm to 2.0 μm, most preferably 1.2 μm to 1.8 μm. This layer may also serve as a transition layer between the second functional layer and the protective layer (when present) to improve the bond between the second functional layer and the protective layer. In the deposition of each layer, the layer may also represent a convenient transition using each of the reactive gases (oxygen, nitrogen) used in the other different layers.
Preferably, the optional transition layer is SiOyNz, where y and z are independently varying integers. In particular examples, SiO γ Nz may be amorphous or crystalline and may have a y value and a z value such that the composition is in SiO2And Si3N4To change between. The value of y is suitably between 0.1 and 3, preferably between 0.1 and 2. The value of z is suitably between 0.1 and 2, preferably between 0.1 and 4/3. The most preferred value of y is 0.5 and the most preferred value of z is 1. Or, z: the ratio of y (i.e. z/y) is from 0.5 to 5, preferably from 1 to 3, most preferably 2.
Products containing such coatings are often used and abused in large quantities and therefore must meet certain manufacturer standards. These prices tend to be higher and higher as the product life is extended. The coating may further comprise one or more additional layers. These may be one or more PVD or CVD layers. These may include chemical layers such as an AFP outermost layer. One known example of this is a fluorine-containing organic layer applied by evaporation. Typically, the additional layer has a thickness of 5nm to 500nm, preferably 5nm to 100nm, most preferably 5nm to 20 nm.
Further specific preferred embodiments of the present invention include or are as described herein substrates, including
Transparent protective layer of silicon dioxide
Transition layer of SiOyNz
Si3N4Functional layer of
Functional layer of TiZrNx
Base material
Further specific preferred embodiments of the present invention include or are as described herein substrates, including
A transparent protective layer of silicon dioxide having a thickness of 1.0 μm to 2.5 μm
A SiOyNz transition layer with a thickness of 0.5 μm to 2.0 μm
Si with a thickness of 40nm-60nm3N4Functional layer
TiZrNx functional layer with thickness of 0.2-1.8 μm
Base material
The substrate to be coated may be a metal, preferably the substrate is zinc, zinc alloy, aluminium alloy, magnesium alloy. The most preferred substrates are zinc and zinc alloys. Typical products to be coated include products made of materials that heretofore could not be easily coated with a carbon-containing coating, such as zinc, magnesium, aluminum, and alloys thereof. Further provided are certain products, e.g., consumer healthcare devices such as shavers and the like, and coated components thereof comprising the present invention.
As shown above, a specific preferred example of the present invention includes the first and second functional layers, the transition layer, and the protective layer, which are all made by sputtering. The coating is deposited in two steps. The first functional layer is deposited in a single chamber, for example, containing Ti and Zr targets and nitrogen as the reactant gases. The second functional layer, the transition layer and the protective layer may all be deposited in a separate chamber with a tunable reactant gas (e.g. nitrogen and oxygen) and with, for example, a Si target. This can be done in multiple chambers with adjacent seals, or in a single chamber with multiple sputtering stations.
The coatings of the present invention can be formed by varying the reactive gases (e.g., nitrogen, oxygen), the target materials (e.g., silicon, titanium, and zirconium), and the layer thicknesses.
The invention also describes a method of making a coated substrate of the invention, comprising depositing a coating on a substrate,
wherein the coating comprises, in order, substantially parallel coatings:
a first functional layer adjacent to the substrate, and
a second functional layer which is a functional layer of a first functional layer,
wherein the first functional layer has a dark appearance and
wherein the second functional layer has a thickness smaller than a wavelength of visible light.
Examples
The invention is now illustrated in the following examples.
The zinc alloy substrate test piece was coated using a sputtering apparatus with different targets (silicon, titanium and zirconium) and nitrogen and oxygen reactive gases.
The test piece is cleaned in deionized water outside the cavity and then enters the cavity, and the air in the chamber is pumped to working pressure. The test piece was then subjected to ion beam cleaning. The cleaned surface was coated with the following materials and thicknesses of coating. In these examples, both matte and polished-side zinc alloys were used as substrates. The color values L, a and b of the coatings were tested using conventional equipment and the results are shown in the following table.
TABLE 1
The coating thickness represents the desired thickness as programmed in the sputter coating installation. In practice, the actual thickness may vary within a tolerance of +/-about 1nm-2 nm.
The uncoated zinc alloy failed the salt spray test within 10 minutes, while the coated matte and polished zinc alloy substrate passed the test even after 4 hours.
In visual inspection, both coatings appeared very black and also passed the internal TP-42 test for resistance to salt water corrosion; the coated matte and polished zinc alloy substrates passed the test for 20 cycles.
Color values L, a and b for the coated substrate are reported below:
TABLE 2
These values correspond to the visual appearance of a very dark substrate observed with the naked eye, both of which are substantially black in daylight.
Thus, the present invention provides very dark and black coatings that do not contain carbon.
Claims (15)
1. A coated substrate comprising a substrate coated with a coating comprising in order substantially parallel layers:
a first functional layer adjacent to the substrate, and
a second functional layer which is a functional layer of a first functional layer,
wherein the first functional layer has a dark appearance and
wherein the second functional layer has a thickness thinner than a wavelength of visible light.
2. The coated substrate of claim 1, wherein the first functional layer has an L value of 55 or less.
3. The coated substrate of any preceding claim, wherein the first functional layer has a and b values of from 10 to-10.
4. The coated substrate of any preceding claim, wherein the first functional layer has a thickness of 0.2 μ ι η to 1.8 μ ι η.
5. The coated substrate of any preceding claim, wherein the second functional layer has a thickness of 40nm to 60 nm.
6. The coated substrate of any preceding claim, wherein the second functional layer comprises Si3N4。
7. The coated substrate of any preceding claim, wherein the second functional layer comprises TiZrNx and wherein x is from 1 to 5.
8. The coated substrate of any preceding claim, wherein there is an outermost protective layer, wherein the protective layer optionally has a thickness of 1.0 μ ι η to 2.5 μ ι η.
9. The coated substrate of claim 8, wherein there is a transition layer between the second functional layer and the protective layer, and optionally wherein the thickness of the over-coating is 0.5 μ ι η to 2.0 μ ι η.
10. The coated substrate of any preceding claim, comprising a substrate coated with a coating comprising, in order, substantially parallel layers:
a TiZrNx functional layer adjacent to the substrate, wherein x is from 1 to 5,
Si3N4a functional layer,
a SiOyNz transition layer, wherein y is 0 to 3, z is 0 to 2, and
SiO2And a protective layer.
11. The coated substrate of any preceding claim, comprising a substrate coated with a coating comprising, in order, substantially parallel layers:
a TiZrNx functional layer adjacent to the substrate having a thickness of 0.2 μm to 1.8 μm, wherein x is 1 to 5,
a Si3N4 functional layer with a thickness of 40nm-60nm,
a SiOyNz transition layer having a thickness of 0.5 μm to 2.0 μm, wherein y is 0 to 3, z is 0 to 2, and
SiO with a thickness of 1.0 μm to 2.5 μm2And a protective layer.
12. The coated substrate of any preceding claim, wherein the substrate is zinc, a zinc alloy, aluminum, an aluminum alloy, magnesium, or a magnesium alloy.
13. A coated substrate according to any preceding claim, wherein the substrate is zinc or a zinc alloy.
14. A product comprising or incorporating a coated substrate as claimed in any preceding claim.
15. The method of preparing a coated substrate according to any one of claims 1-13, comprising depositing a coating onto a substrate,
wherein the coating comprises in sequence substantially parallel layers:
a first functional layer adjacent to the substrate, and
a second functional layer which is a functional layer of a first functional layer,
wherein the first functional layer has a dark appearance and
Wherein the second functional layer has a thickness thinner than a wavelength of visible light.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0514119D0 (en) * | 2005-07-09 | 2005-08-17 | Pilkington Plc | Heat treatable coated glass pane and process for the manufacture thereof |
| CN101637986A (en) * | 2008-07-30 | 2010-02-03 | 比亚迪股份有限公司 | Color material |
| CN101733984A (en) * | 2008-11-07 | 2010-06-16 | 马斯科公司 | Coated article with black color |
| TW201122123A (en) * | 2009-12-30 | 2011-07-01 | Hon Hai Prec Ind Co Ltd | Colorized casing |
| CN103017383A (en) * | 2012-11-30 | 2013-04-03 | 中国科学院上海技术物理研究所 | Solar selective absorption film system with adjustable color and preparation method thereof |
| CN104029447A (en) * | 2013-03-08 | 2014-09-10 | 韦伯科技有限公司 | Coated Article With Dark Color |
| US20140315014A1 (en) * | 2013-03-08 | 2014-10-23 | Vapor Technologies, Inc. | Coated Article Having A Vivid Color |
| CN109639860A (en) * | 2018-12-17 | 2019-04-16 | 佛山市易晟达科技有限公司 | A kind of cover board |
| CN110373645A (en) * | 2019-07-31 | 2019-10-25 | 深圳森丰真空镀膜有限公司 | A kind of super black wear-resistant coating and preparation method thereof |
| CN110484862A (en) * | 2018-05-15 | 2019-11-22 | 蓝思科技（长沙）有限公司 | Composite coating Logo and preparation method thereof with include its ceramic cover plate and electronic equipment |
| US20200024185A1 (en) * | 2017-04-17 | 2020-01-23 | Kcc Corporation | Laminated System |
| CN111247457A (en) * | 2017-08-31 | 2020-06-05 | 康宁股份有限公司 | Hybrid gradient interference hard coating |
-
2021
- 2021-04-06 CN CN202110370178.5A patent/CN113549872B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0514119D0 (en) * | 2005-07-09 | 2005-08-17 | Pilkington Plc | Heat treatable coated glass pane and process for the manufacture thereof |
| CN101637986A (en) * | 2008-07-30 | 2010-02-03 | 比亚迪股份有限公司 | Color material |
| CN101733984A (en) * | 2008-11-07 | 2010-06-16 | 马斯科公司 | Coated article with black color |
| TW201122123A (en) * | 2009-12-30 | 2011-07-01 | Hon Hai Prec Ind Co Ltd | Colorized casing |
| CN103017383A (en) * | 2012-11-30 | 2013-04-03 | 中国科学院上海技术物理研究所 | Solar selective absorption film system with adjustable color and preparation method thereof |
| US20140255673A1 (en) * | 2013-03-08 | 2014-09-11 | Vapor Technologies, Inc. | Coated Article With Dark Color |
| CN104029447A (en) * | 2013-03-08 | 2014-09-10 | 韦伯科技有限公司 | Coated Article With Dark Color |
| US20140315014A1 (en) * | 2013-03-08 | 2014-10-23 | Vapor Technologies, Inc. | Coated Article Having A Vivid Color |
| US20200024185A1 (en) * | 2017-04-17 | 2020-01-23 | Kcc Corporation | Laminated System |
| CN111247457A (en) * | 2017-08-31 | 2020-06-05 | 康宁股份有限公司 | Hybrid gradient interference hard coating |
| CN110484862A (en) * | 2018-05-15 | 2019-11-22 | 蓝思科技（长沙）有限公司 | Composite coating Logo and preparation method thereof with include its ceramic cover plate and electronic equipment |
| CN109639860A (en) * | 2018-12-17 | 2019-04-16 | 佛山市易晟达科技有限公司 | A kind of cover board |
| CN110373645A (en) * | 2019-07-31 | 2019-10-25 | 深圳森丰真空镀膜有限公司 | A kind of super black wear-resistant coating and preparation method thereof |
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