CN101784692B - Process for manufacturing multi-layered thin film by dry vacuum vapor deposition - Google Patents
Process for manufacturing multi-layered thin film by dry vacuum vapor deposition Download PDFInfo
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Images
Classifications
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Laminated Bodies (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
The present invention relates to a process for manufacturing multi-layered thin film by using dry vacuum vapor deposition, in particular, a process for manufacturing multi- layered thin film by using stable and simple dry vacuum vapor deposition, the process being capable of providing optical beautifulness and luxury impression to cases, windows, keypads, function key parts, various accessory parts or the like for mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc.
Description
Technical field
The present invention relates to by using dry vacuum vapor deposition to make the method for multilayer film, especially, it relates to by using stable and simple dry vacuum vapor deposition to make the method for multilayer film, and the method can and show that for portable type electronic product such as mobile telephone, MP3 player, portable media player (PMP), DMB (DMB) receiving set, auto-navigation system, notebook computer etc. the shell, window, keyboard, navigation key feature, various accessory components etc. of product provide visual aesthetic feeling and luxurious impression.
Background technology
Portable type electronic product such as mobile telephone, the MP3 player, portable media player (PMP), DMB (DMB) receiving set, auto-navigation system, notebook computer etc. and demonstration product such as watch-dog, touch-screens etc. use shell, window, keyboard, navigation key feature, various accessory components etc., they are by metal, glass, acryl (acryl) (acrylic resin), polycarbonate (PC), polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), injection moulded products or the sheet plate form of acronitrile-butadiene-styrene (ABS) copolymer resin and combination preparation thereof.For these parts, use the vacuum vapor deposition of metal and/or metal oxide to apply, so that visual aesthetic feeling and luxurious impression to be provided.
In the shell of mobile telephone, especially, for the stability of communication quality, by carrying out the vacuum vapor deposition method with metal oxide rather than metal, on the front and back of its shell, window, keyboard, the integrated shell of window etc., form the dielectric thin film coatings of non-conduction.
Yet, because the metal and/or the metal oxide film that apply by the vacuum vapor deposition method are low to the adhesion strength of matrix, therefore it demonstrates low resistance to abrasion, scrath resistance and pencil hardness, and owing to the film of vacuum vapor deposition breaks away from high temperature, high humidity and salt solution, so its reliability also is difficult to guarantee.
Therefore, in order to solve the problem such as reliability, before vapor deposition processes and undertaken by wet methods such as dipping, spraying, spin coating, ink jet printing afterwards that UV applies or hard the coating.
Especially, if for being used for the shell of electronic product, window, the sheet plate form of keyboard etc. or by acryl, polycarbonate (PC), polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), the injection moulded products of acronitrile-butadiene-styrene (ABS) copolymer resin or its combination preparation provides Vision Design and introduces the vacuum vapor deposition method, then for adhesion strength and the stability of vapor deposition layer, should pass through to use such as pickling process, spraying method, spin-coating method, the independently wet method of ink jet printing method etc. realizes that the bottom applies and top coating.Yet, in this case, because wet method and vaccum gas phase sedimentation method carry out in the mode that replaces, cause the additional cost because using diverse ways to bring, and cause between different methods In transit the problem of substandard products to occur.
That is to say, owing to introduced wet method, wet method and vaccum gas phase sedimentation method (dry method) carry out in the mode that replaces, and the process period that therefore is used for application member is elongated, and this is because will repeat to apply in transportation between the different methods and each method the installation and removal of object.
In addition, because the processing substandard products that during different methods carries out, produce and the high fraction defective that In transit produces between different methods, and because the increase of the production time that multi-method causes all causes productive rate to descend, productive rate descends and causes again high products production cost.
In addition, when the company that carries out wet coating and the company that carries out vacuum vapor deposition not simultaneously, this type of structure problem has the tendency that becomes more serious.
In addition, as shown in Figure 4, with 70 compare by filming of hundreds and thousands of vacuum vapor deposition processes (dry method) preparations, 60 thicker filming of product 10 surface preparation by wet method, and because the reduction of matrix visual characteristics and superficial makings is deteriorated, the unique property of matrix can not reach its best.
Summary of the invention
Technical purpose
Solution as the problems referred to above in the prior art, the purpose of this invention is to provide the method for making multilayer film, the method is passed through the front and back at the shell of electronic product, window, keyboard, navigation key feature, forming stable vacuum vapor deposition film on the integrated shell of window and the various attaching substrate carries out, even the minimum as far as possible dry vacuum vapor deposition step of the vacuum vapor deposition apparatus by needs is carried out, the method can and show that for portable type electronic product product provides attractive in appearance and luxurious Vision Design, and the reliability that ensures product.
In addition, thereby other purpose of the present invention is by eliminating or minimize the effect that the environment-conscious wet method obtains elimination or environmental contamination reduction, and obtain because the cost savings effect that the minimizing of production time and substandard products brings by the reliability that guarantees film, even simplify as far as possible the method according to demand.
Technical scheme
According to the present invention, be provided for making the method for multilayer film, the method is included in and forms the step that the bottom applies the step of vapor deposition layer and applies vapor deposition layer formation vision coating in this bottom on the matrix, wherein this bottom coating vapor deposition layer provides the adhesion strength between matrix and the vision coating, and wherein these multilayer film form by dry vacuum vapor deposition.
Method of the present invention preferably also comprises the step that forms middle coating vapor deposition layer after the step that forms the vision coating.
In addition, method of the present invention preferably also comprises the step that forms the top coating vapor deposition layer after the step of coating vapor deposition layer or after the step that forms the vision coating in the middle of forming.
According to a further aspect in the invention, the multilayer film coating is provided, it forms by the method for the manufacture of multilayer film of the present invention, and is included in the vision coating that the bottom that forms on the matrix applies vapor deposition layer and forms at this bottom coating vapor deposition layer.
Multilayer film coating of the present invention preferably also is included in the middle vapor deposition layer that applies that forms on the vision coating.
In the middle of preferably also being included in, multilayer film coating of the present invention applies the top coating vapor deposition layer that forms on the vapor deposition layer.
Multilayer film coating of the present invention preferably also is included in the top coating vapor deposition layer that forms on the vision coating.
According to a further aspect in the invention, provide electronic product, it comprises the multilayer film coating by the method formation of manufacturing multilayer film of the present invention.
Beneficial effect
If the shell that is used for applying portable type electronic product for the manufacture of the dry vacuum vapor deposition method of multilayer film of the present invention, window, the integrated shell of window, keyboard, the integrated window of keyboard, navigation key feature, various appurtenances etc., described portable type electronic product is mobile telephone for example, the MP3 player, portable media player (PMP), DMB (DMB) receiving set, auto-navigation system, notebook computer etc. and demonstration product such as watch-dog, touch-screen etc. and domestic electronic appliances such as refrigerator, air-conditioning, TV etc., then when attractive in appearance and luxurious Vision Design was provided for these products, the reliability of product also can be protected.
In addition, can the environment-conscious wet method obtains to eliminate or the effect of environmental contamination reduction by eliminating or minimizing, and obtain because the cost savings effect that the minimizing of production time and substandard products brings by the reliability that guarantees film, even simplify as far as possible the method according to demand.
The accompanying drawing summary
Fig. 1 is the process flow sheet of an embodiment of the vacuum vapor deposition method for the manufacture of multilayer film of the present invention.
Fig. 2 is the composition synoptic diagram according to the vacuum vapor deposition multilayer film of one embodiment of the invention manufacturing.
Fig. 3 is the description figure of adhesion strength and surface contact angle Relations Among.
Fig. 4 is the bottom that forms of the wet method by routine and Topcoating and those the comparison diagram of thickness that forms by vaccum gas phase sedimentation method of the present invention.
The photo of Fig. 5 has shown the surface contact angle of (in-mold) injection-molded product in the plastic mold.
The photo of Fig. 6 has shown in a kind of embodiment according to the present invention makes in the multilayer film surface contact angle behind the vacuum vapor deposition of bottom coating.
The photo of Fig. 7 has shown in a kind of embodiment according to the present invention makes in the multilayer film surface contact angle behind the vacuum vapor deposition of having finished top coating.
* the mark that shows among the figure
10: matrix
20: the bottom applies vapor deposition layer
30: the vision coating
40: the middle vapor deposition layer that applies
50: the top coating vapor deposition layer
60: according to the coating of conventional wet method
70: according to the vacuum vapor deposition multilayer film of dry method of the present invention
Embodiment
Compare with the conventional coating that provides by wet method, the vacuum vapor deposition method for the manufacture of film of the present invention is characterised in that this coating forms in vacuum phase deposition equipment by dry method.The conventional coating that provides by wet method at present can comprise, for example, UV (ultraviolet ray) sclerotic type coating, is used for improving the base coat of the adhesion strength between matrix and the vision coating, and for the protection of the Topcoating of vision single or multiple lift coating.
In vacuum vapor deposition method of the present invention (dry method), employing is used to form the chemical reagent of each thin film layer, in vacuum phase deposition equipment, provide stable single or multiple lift coating by ultra-thin coating method, the preferred carrier that uses as in korean patent application No.10-2007-0075000, describe.
The suitable matrix that can use film-forming method of the present invention comprises, but be not limited to, the shell of portable type electronic product, window, the integrated shell of window, keyboard, the integrated window of keyboard, navigation key feature and various appurtenances, described portable type electronic product such as mobile telephone, MP3 player, portable media player (PMP), DMB (DMB) receiving set, auto-navigation system, notebook computer etc. and demonstration product such as watch-dog, touch-screen etc.Matrix can be sheet plate form or various injection moulded products form, but is not limited to this.
Metal, glass, acryl (acrylic resin), polycarbonate (PC), polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), acronitrile-butadiene-styrene (ABS) copolymer resin and combination thereof can be used as substrate material, but are not limited to this.
In film-forming method of the present invention, applying vapor deposition layer in the bottom that matrix forms is for the layer that adhesion strength is provided between the vision coating of matrix and subsequently formation.Preferably, coating vapor deposition layer in the bottom of formation has
Extremely
The nano level minimal thickness of (1nm to 100nm), and serve as so-called " nanometer priming paint " to increase the adhesion strength between stromal surface and the vision individual layer that in later step, forms or the overbrushing layer.
In addition, according to the Multi-layer design of surface property and the vision coating of matrix, in the vacuum vapor deposition method, this bottom apply vapor deposition layer can pass through plasmaassisted CVD (Chemical Vapor Deposition) method (ion is assisted) with
Extremely
Thickness deposition, and therefore can demonstrate the hard coat feature and improve the attachment characteristic of this thin film vapor deposition layer.
Preferably, as the coated agent that forms bottom coating vapor deposition layer, can use have one or more functional groups that are selected from carboxyl, phosphate, silylation, amido, hydroxyl, aldehyde radical, ketone group, ether and ketal group based on carbon compound, and its molecular weight can be 100-10,000, but be not limited to this.
In film-forming method of the present invention, applying the vision coating that vapor deposition layer forms in the bottom can be single or multiple lift, and attractive in appearance and luxurious Vision Design, shades of colour and mirror image or the effect of anti-mirror image can be provided for the outward appearance of product (being matrix).
Material as forming the vision coating can use metal such as SUS (stainless steel), nickel (Ni), aluminium (Al), chromium (Cr), tin (Sn), indium-Xi (In-Sn) etc.; Metal oxide such as silicon-dioxide (SiO
2), titanium dioxide (TiO
2), aluminum oxide (Al
2O
3), zirconium white (ZrO
2), Indium sesquioxide titanium (In
xTi
yO
2, ITO), barium oxide titanium (BaTiO
3), magnesium oxide (MgO) etc.; Metal nitride such as SiN, TiN etc.; Or metal fluoride such as MgF
2Deng.In vacuum phase deposition equipment, these materials are by using the vaporization of electron beam or resistance heating device and being deposited as individual layer or forming multilayer in the mode that replaces.Thickness to the vision coating does not have particular restriction.For example, it can form individual layer with different thickness or the multilayer of individual layer, for example exists
Nanometer grade thickness (1nm-100nm) is to the micron order thickness range.
According to a preferred embodiment of the invention, after the step that forms the vision coating, apply vapor deposition layer in the middle of also can forming from the teeth outwards.The middle vapor deposition layer that applies plays the effect that strengthens anti-salt water-based, resistance to abrasion, scrath resistance etc. and the function of assisting the top coating vapor deposition layer that can additionally form.
According to surface property and the Multi-layer design of vision coating, can in the vacuum vapor deposition method, pass through plasmaassisted CVD (Chemical Vapor Deposition) method (ion auxiliary) with
Thickness deposition in the middle of apply vapor deposition layer, and weak scrath resistance that therefore can the enhanced film vapor deposition layer, anti-salt water-based etc.
Preferably, as the coated agent that applies vapor deposition layer in the middle of being used to form, can use have one or more functional groups that are selected from carboxyl, phosphate, silylation, amido, hydroxyl, aldehyde radical, ketone group, ether and ketal group based on carbon compound, and its molecular weight can be 100-10,000, but be not limited to this.
According to a preferred embodiment of the invention, in the middle of forming, apply after the step of vapor deposition layer, also can further form from the teeth outwards the top coating vapor deposition layer.The top coating vapor deposition layer pollutes resistance (anti-fingerprint) and characteristic easy to clean and strengthens reliability such as anti-salt water-based, resistance to abrasion, scrath resistance etc. by providing, thereby plays the effect of protecting the vision coating.
Apply surface property and the Multi-layer design of vapor deposition layer according to the centre, in the vacuum vapor deposition method, the top coating vapor deposition layer can pass through plasmaassisted CVD (Chemical Vapor Deposition) method (ion is assisted) with
Thickness deposition.
Preferably, as the coated agent that is used to form the top coating vapor deposition layer, can use have one or more functional groups that are selected from carboxyl, phosphate, silylation, amido, hydroxyl, aldehyde radical, ketone group, ether and ketal group based on the fluorine carbon compound, and its molecular weight can be 100-10,000, but be not limited to this.
In the present invention, the coated agent that is used to form each thin film layer can deposit by using electron beam, resistance heating device, sputtering equipment or ion plating apparatus, preferably uses such as the carrier described in the korean patent application No.10-2007-0075000.
In addition, preferably in the present invention, the formation of multilayer film structure is carried out in vacuum phase deposition equipment continuously.
The coated agent that is used to form each thin film layer preferably comprises for storing and the solvent of reagent stability described solvent such as water, methyl alcohol, ethanol, acetone, methyl ethyl diketone, ethylene glycol, ketone etc.
Method for the manufacture of the vacuum vapor deposition multilayer film according to the present invention will be with below at length progressively explanation of specific embodiment.
According to embodiment of the method for the manufacture of the vacuum vapor deposition multilayer film of the present invention with consistent shown in Fig. 1.Process flow sheet according to shown in Figure 1 the invention is characterized in, in vacuum phase deposition equipment, is all undertaken by dry method vacuum phase deposition equipment from all coating operations that are installed to dismounting of matrix (being product).
1: installation steps
To be installed in the vacuum phase deposition equipment such as the matrix (or product) 10 of the integrated shell of shell, window, window, keyboard, the integrated window of keyboard, navigation key feature and the various appurtenances of portable type electronic product wherein said portable type electronic product such as mobile telephone, MP3 player, portable media player (PMP), DMB (DMB) receiving set, auto-navigation system, notebook computer etc. and show product such as watch-dog, touch-screen etc.For avoiding matrix during vacuum vapor deposition process, to come off, this matrix is installed on the anchor clamps, described jig Design is become to be fit to various forms of matrix.
2: steps of exhausting
When after the installation of matrix in vacuum phase deposition equipment, to carrying out exhaust in the vacuum vapor deposition cavity to keep 1.0 * 10
-6-1.0 * 10
-3The high vacuum state of holder, preferred 1.0 * 10
-5The high vacuum state of holder or higher vacuum apply to carry out vacuum vapor deposition with metal and/or metal oxide.According to the material of installation matrix 10, the temperature setting in the vacuum vapor deposition cavity is set to 20-300 ℃.
3: the vapor deposition step of base coat
When having obtained suitable high vacuum state, at argon (Ar), nitrogen (N
2) and oxygen (O
2) under the air-flow by using ion beam apparatus to carry out electrion, to produce the plasma body of corresponding gas.According to the surface condition of installation matrix, use energetic plasma gas 10 seconds to 1,000 second, with the surface (plasma etching) of the activation matrix of being installed 10.
Form the bottom on matrix 10 activated surfaces and apply vapor deposition layer 20.Apply vapor deposition layer in order to form this bottom, can use such as the carrier described at korean patent application No.10-2007-0075000.In this carrier, be written into the reagent that applies for the bottom and subsequently this carrier be mounted to vaporization mouth or the resistive heating type vaporization mouth that vacuum phase deposition equipment uses electron beam, and subsequently by using the heating of electron beam or resistance-heated boat to be mounted to the carrier of vaporization mouth, with the coated agent of vaporizing and in carrier, loading, and form bottom coating vapor deposition layer.
In the situation of electron beam hot type, can make the in steps automatization of coating procedure by using IC-5 (INFICON), wherein said IC-5 (INFICON) is a kind of operating device for vacuum phase deposition equipment.The power (power) of electron beam is controlled between 1.5% to 8.0% suitably, preferably between 2.0% to 4.0%.
The bottom that as above forms like that applies vapor deposition layer preferably to have
The thickness of (0.001 μ m to 0.1 μ m), most preferably from about
(0.01 μ m, 10nm) or more or less.Can use aforesaid plasma etching 0 to 300 second on it, but stable base applies vapor deposition layer thus.
The coating that forms on the stromal surface is relevant with surface energy.Can estimate adhesion strength by measuring matrix and the contact angle between the water droplet on this stromal surface, as shown in Figure 3.When contact angle diminished, it is large that adhesion strength becomes.
In plastic mold in the situation of injection-molded product, contact angle before applying on the stromal surface is 74.3 ° (Fig. 5), and apply vapor deposition layer 20 after product surface forms in the bottom, this contact angle is down to 32.2 ° (Fig. 6), and before the bottom applies vapour deposition and afterwards, surface energy changes to 47.98mN/m from 33.02mN/m.That is to say that adhesion strength applies vapour deposition by the bottom and is improved.
For the product surface of differing materials, following table 1 and table 2 have shown that respectively applying vapor deposition layer in the bottom forms front and back, the variation of surface contact angle and surface energy.
Table 1 base coat forms the variation of front and rear surfaces contact angle
Table 2 base coat forms the variation of front and rear surfaces energy
4: many vapor deposition step (vision coating formation step)
For attractive in appearance and luxurious Vision Design is provided to matrix, and show distinct colors, mirror image or non-mirror effect and anti-reflection effect, apply vapor deposition layer in the bottom and form vision coating 30.
In vacuum phase deposition equipment, use electron beam or resistance heating device, by vapour deposition alternately with single or multiple lift, with metal such as SUS (stainless steel), nickel (Ni), aluminium (Al), chromium (Cr), tin (Sn), indium-Xi (In-Sn) etc.; Metal oxide such as silicon-dioxide (SiO
2), titanium dioxide (TiO
2), aluminum oxide (Al
2O
3), zirconium white (ZrO
2), Indium sesquioxide titanium (In
xTi
yO
2, ITO), barium oxide titanium (BaTiO
3), magnesium oxide (MgO) etc.; Metal nitride such as SiN, TiN etc.; Or metal fluoride such as MgF
2Deng, carry out vapour deposition, thereby form vision coating 30.
5: the vapor deposition step of inter coat
Because vision coating 30 is formed by metal, metal oxide, metal nitride or metal fluoride, because the characteristic of inorganic materials, so it has various surface property and to vulnerability moist and that pollute etc.
Therefore, on vision coating 30, according to different surface conditions, preferably with about
About thickness apply vapor deposition layer 40 in the middle of forming, so that the surface to various ambient stables to be provided, and strengthen the reliability of abrasion resistance and vacuum vapor deposition film Antagonistic Environment.
Multi-layer design according to the vision coating, can in vacuum vapor deposition process, apply vapor deposition layer 40 in the middle of CVD (Chemical Vapor Deposition) method (ion the is auxiliary) deposition by plasmaassisted, and therefore can show hard coating characteristic and strengthen the weak scrath resistance of thin film vapor deposition layer, anti-salt water-based etc.
The same with bottom coating vapor deposition layer, apply vapor deposition layer in the middle of can forming with the carrier described in korean patent application No.10-2007-0075000.In this carrier, be written into the reagent that applies for this centre, and in vacuum phase deposition equipment, this carrier is mounted to subsequently the vaporization mouth that uses electron beam or the vaporization of resistive heating type mouthful, then be loaded in coated agent in this carrier by using electron beam or resistance-heated boat to heat this carrier that is mounted to vaporization mouthful with vaporization, and form this centre coating vapor deposition layer.
Applying vapor deposition layer in the middle of as above forming like that preferably has
The thickness of (0.001 μ mt to 0.1 μ m), most preferably from about
(0.01 μ m, 10nm) or more or less.Can use aforesaid plasma etching 0 to 300 second on it, apply vapor deposition layer in the middle of can stablizing thus.
6: the vapor deposition step of Topcoating
As mentioned above, because the characteristic of inorganic materials, vision coating 30 has various surface property and to vulnerability moist and that pollute etc., thus top coating vapor deposition layer 50 preferably directly overlays on the vision coating 30 or insert betwixt in the middle of apply vapor deposition layer 40.
Can coat-thickness not carried out in the situation of special control by forming top coating vapor deposition layer 50 with bottom and the middle similar method of vapor deposition layer that applies, its thickness is
The film coating that forms by the top coating vapor deposition step has the feature of low-down surface energy and low-friction coefficient, therefore demonstrates very smooth surface property, and therefore can reduce significantly adhering to of source of pollution such as fingerprint and dirt.Even adhered to fingerprint and dirt, also can remove by the function easy to clean of this coating excellence at an easy rate.And, simultaneously, can obtain peculiar characteristics such as waterproof or grease proofing characteristic, scrath resistance, wearing quality, and therefore can be formed on stable vacuum vapor deposition coating after the reliability testing of the product with exterior coating and coated inside.
As shown in Figure 3, when contact angle becomes large, adhere to or the adhesion strength variation.Yet aspect the adhering to of pollutent, it means that the resistance to polluting becomes stronger.Shown in Figure 7 is the coated surface with top coating vapor deposition layer of processing with aforesaid method.Following table 3 and 4 has shown respectively contact angle and the surface energy when forming the top coating vapor deposition layer.
Contact angle when table 3 forms the top coating vapor deposition layer
Surface energy when table 4 forms the top coating vapor deposition layer
7: aeration step (the broken ring of vacuum step)
When having finished the manufacturing of the multilayer film that pass through dry method, the vacuum state in the broken ring vacuum phase deposition equipment.
8: demounting procedure
Broken encircled the vacuum state in the vacuum phase deposition equipment after, the product of having finished the multilayer film manufacturings is taken out from vacuum phase deposition equipment.
According to above-mentioned embodiment of the present invention, the present invention has been carried out detailed explanation.Yet, should be appreciated that above-mentioned embodiment never means to limit the scope of the present invention.
Industrial applicibility
The present invention can be applicable to portable type electronic product such as mobile telephone, MP3 player, portable media player (PMP), DMB (DMB) receiving set, auto-navigation system, notebook computer etc. and show product such as watch-dog, touch-screen etc. and household electrical appliance such as refrigerator, air-conditioning, TV etc. in the integrated shell of shell, window, window, keyboard, the integrated window of keyboard, navigation key feature, the various annexes of indicating meter etc. and the appurtenances of use.
Claims (17)
1. make the method for multilayer film, may further comprise the steps: form the bottom in matrix and apply vapor deposition layer; And in this bottom coating vapor deposition layer formation vision coating, wherein this bottom applies vapor deposition layer for providing adhesion strength between matrix and the vision coating, its mesostroma is by being selected from metal, glass, acryl, polycarbonate, PMMA, PET, the material of ABS resin and combination thereof is made, the bottom applies vapor deposition layer by having one or more carboxyls that are selected from, phosphate, silylation, amido, hydroxyl, aldehyde radical, ketone group, the functional group of ether and ketal group forms based on carbon compound
Wherein the formation of all layers in these multilayer film be undertaken by dry vacuum vapor deposition and the bottom apply vapor deposition layer and have
Thickness.
2. the method for claim 1 also comprises the step that applies vapor deposition layer in the middle of forming after the step that forms the vision coating.
3. the method for claim 2 also comprises the step that forms the top coating vapor deposition layer after the step of coating vapor deposition layer in the middle of forming.
4. the method for claim 1 also comprises the step that forms the top coating vapor deposition layer after the step that forms the vision coating.
5. the process of claim 1 wherein that matrix is portable type electronic product, the integrated shell of shell, window, window, keyboard, the integrated window of keyboard, navigation key feature or the appurtenances that show product or household electrical appliance.
6. the process of claim 1 wherein that the vision coating is formed by the material that is selected from metal, metal oxide, metal nitride, metal fluoride and combination thereof.
7. the method for claim 2 applies vapor deposition layer in the middle of wherein by having forming based on carbon compound of one or more functional groups that are selected from carboxyl, phosphate, silylation, amido, hydroxyl, aldehyde radical, ketone group, ether and ketal group.
8. the method for claim 3, wherein the top coating vapor deposition layer is by having forming based on the fluorine carbon compound of one or more functional groups that are selected from carboxyl, phosphate, silylation, amido, hydroxyl, aldehyde radical, ketone group, ether and ketal group.
9. the process of claim 1 wherein that vacuum vapor deposition is by using electron beam, resistance heating device, sputtering equipment or ion plating apparatus to carry out.
10. the process of claim 1 wherein that being formed in the vacuum phase deposition equipment of multilayer film structure carry out continuously.
11. the multilayer film coating, its method one of any in according to claim 1-10 forms, and is included in the bottom that forms on the matrix and applies vapor deposition layer, and the vision coating that forms at this bottom coating vapor deposition layer.
12. the multilayer film coating of claim 11 also is included in the middle vapor deposition layer that applies that forms on the vision coating.
13. the multilayer film coating of claim 12 applies the top coating vapor deposition layer that forms on the vapor deposition layer in the middle of also being included in.
14. the multilayer film coating of claim 11 also is included in the top coating vapor deposition layer that forms on the vision coating.
15. comprise the electronic product of the multilayer film coating that forms by either method among the claim 1-10.
16. the electronic product of claim 15, this electronic product are mobile telephone, MP3 player, portable media player (PMP), DMB (DMB) receiving set, auto-navigation system, notebook computer, watch-dog, touch-screen, refrigerator, air-conditioning or TV.
17. the electronic product of claim 15, wherein this multilayer film coating forms at shell, window, the integrated shell of window, keyboard, the integrated window of keyboard, navigation key feature or appurtenances.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20070077906 | 2007-08-02 | ||
| KR10-2007-0077906 | 2007-08-02 | ||
| PCT/KR2008/004470 WO2009017376A2 (en) | 2007-08-02 | 2008-07-31 | Process for manufacturing multi-layered thin film by dry vacuum vapor deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101784692A CN101784692A (en) | 2010-07-21 |
| CN101784692B true CN101784692B (en) | 2013-03-20 |
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| CN2008801016616A Active CN101784692B (en) | 2007-08-02 | 2008-07-31 | Process for manufacturing multi-layered thin film by dry vacuum vapor deposition |
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| Country | Link |
|---|---|
| JP (1) | JP2010535286A (en) |
| KR (2) | KR101824017B1 (en) |
| CN (1) | CN101784692B (en) |
| HK (1) | HK1145192A1 (en) |
| WO (1) | WO2009017376A2 (en) |
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| KR101246022B1 (en) * | 2010-08-19 | 2013-04-02 | (주)에스아이티 | Display window panel for anti-reflection and method thereof |
| US9339993B2 (en) | 2010-09-14 | 2016-05-17 | Corning Incorporated | Appliance fascia and mounting therefore |
| KR101690091B1 (en) * | 2015-04-16 | 2016-12-27 | 주식회사 쎄코 | Antibacterial primer coating agent for vacuum deposition and method of multi-layered coating by using the same |
| KR102468988B1 (en) | 2020-07-14 | 2022-11-22 | 주식회사 동남티에스 | Method for forming decorative pattern by metal deposition layer and plastic decorative member including the decorative pattern by the same method |
Citations (1)
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| CN1432661A (en) * | 2002-01-10 | 2003-07-30 | 日本电工株式会社 | Metal layer forming process and laminated metal foil-based product |
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| JPH03273201A (en) * | 1990-03-23 | 1991-12-04 | Asahi Optical Co Ltd | Surface high-reflection mirror |
| JP2748066B2 (en) * | 1992-04-23 | 1998-05-06 | 富士写真光機株式会社 | Reflector |
| JP3352172B2 (en) * | 1993-08-30 | 2002-12-03 | キヤノン株式会社 | Optical thin film of plastic optical component and method of forming the same |
| JP2000108262A (en) * | 1998-10-09 | 2000-04-18 | Toray Ind Inc | Polypropylene film for metal deposition and metal- deposited polypropylene film |
| US6958748B1 (en) * | 1999-04-20 | 2005-10-25 | Matsushita Electric Industrial Co., Ltd. | Transparent board with conductive multi-layer antireflection films, transparent touch panel using this transparent board with multi-layer antireflection films, and electronic equipment with this transparent touch panel |
| JP2000328231A (en) * | 1999-05-20 | 2000-11-28 | Toray Ind Inc | Deposition method by organic material to be deposited by evaporation |
| JP4482971B2 (en) * | 1999-09-08 | 2010-06-16 | 株式会社ニコン | Reflector |
| JP3415801B2 (en) * | 2000-02-21 | 2003-06-09 | 三容真空工業株式会社 | Organic coating method and apparatus |
| JP4023065B2 (en) * | 2000-03-23 | 2007-12-19 | 凸版印刷株式会社 | Anti-reflective member |
| JP2003255133A (en) * | 2002-03-05 | 2003-09-10 | Yazaki Corp | Combiner and its manufacturing method, and display device for vehicle |
| KR20030073733A (en) * | 2002-03-13 | 2003-09-19 | 주식회사 뮤렉스테크놀로지 | Metal Sputtering and Evaporation Equipment and Method on Plastics |
| KR100514953B1 (en) * | 2003-03-05 | 2005-09-14 | 주식회사 피앤아이 | Method for fabricating plastic housing of electronic article |
| JP2005169995A (en) * | 2003-12-15 | 2005-06-30 | Dainippon Printing Co Ltd | Gas barrier sheet and adhesiveness improved sheet |
| JP4888990B2 (en) * | 2004-10-26 | 2012-02-29 | 尾池工業株式会社 | Reflector for backlight device |
| JP3756171B1 (en) * | 2004-10-28 | 2006-03-15 | 尾池工業株式会社 | Method for producing metal-deposited film with antioxidant layer and metal-deposited film with antioxidant layer |
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2008
- 2008-07-31 WO PCT/KR2008/004470 patent/WO2009017376A2/en active Application Filing
- 2008-07-31 CN CN2008801016616A patent/CN101784692B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432661A (en) * | 2002-01-10 | 2003-07-30 | 日本电工株式会社 | Metal layer forming process and laminated metal foil-based product |
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| KR101824017B1 (en) | 2018-02-01 |
| KR20160064051A (en) | 2016-06-07 |
| HK1145192A1 (en) | 2011-04-08 |
| CN101784692A (en) | 2010-07-21 |
| WO2009017376A3 (en) | 2009-04-16 |
| WO2009017376A2 (en) | 2009-02-05 |
| KR20090013719A (en) | 2009-02-05 |
| JP2010535286A (en) | 2010-11-18 |
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