CN114981077A - Metallized film and method for manufacturing same - Google Patents
Metallized film and method for manufacturing same Download PDFInfo
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- CN114981077A CN114981077A CN202180010047.4A CN202180010047A CN114981077A CN 114981077 A CN114981077 A CN 114981077A CN 202180010047 A CN202180010047 A CN 202180010047A CN 114981077 A CN114981077 A CN 114981077A
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- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000010949 copper Substances 0.000 claims abstract description 97
- 229910052802 copper Inorganic materials 0.000 claims abstract description 96
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 43
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
-
- 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
- C23C14/14—Metallic material, boron or silicon
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic 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
- C23C14/58—After-treatment
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The subject of the invention is to obtain a metallized film with small change of resistance and chroma before and after the implementation of a humidity resistance test, and a manufacturing method thereof. The metallized film is characterized in that the metallized film comprises a copper layer and a rust-preventive layer on at least one surface of the film in this order from the film side, wherein the rust-preventive layer comprises at least one selected from the group consisting of metallic titanium, titanium oxide, and a mixture thereof, the metallized film has a surface resistance change rate of 20% or less after 3 days in an 85 ℃ RH atmosphere, and a color difference Delta E of 6.5 or less after 3 days in the atmosphere.
Description
Technical Field
The present invention relates to a metallized film and a method for manufacturing the metallized film.
Background
Metallized films are used as conductive materials in a wide range of fields such as film capacitors, electromagnetic wave shields, battery collectors, and printed circuit boards.
For example, in recent years, high performance and multi-functionalization of semiconductor integrated circuit devices (hereinafter, sometimes referred to as "semiconductor devices") used as microprocessors and the like of computers have been advanced. Therefore, the pitch between terminals of the semiconductor element is required to be narrow, and the wiring pattern is also required to be fine as a package substrate of a printed wiring board on which the semiconductor element is mounted, and low-resistance copper is suitably used.
A method for forming a wiring pattern of a printed wiring board is manufactured by etching a copper film of a copper-clad laminate. Examples of the processing method by etching include a removal method and a semi-addition method. The removal method is a method of forming a circuit by removing an unnecessary copper film portion from a copper-clad laminate, and is a method of forming a necessary circuit by applying ink or paint to a portion to be left as a wiring, and etching the copper film with a chemical corrosive to a metal. On the other hand, the semi-additive method is a method of adding a circuit pattern on an insulating layer substrate in the subsequent step, and is a method of forming a pattern by forming a resist on a portion where no pattern is formed and performing plating.
In recent years, printed wiring boards to be mounted on electronic devices and the like to achieve reduction in size and weight have been required to form fine pitch circuits in order to increase component mounting density and to arrange the components in a narrow area.
In order to satisfy these requirements, a copper foil or a metallized film is preferably used as the wiring material, and a metallized film having a reduced copper film thickness is preferably used (for example, patent document 1).
In a mobile communication device, an electromagnetic wave shielding film has been conventionally laminated on a wiring portion and a chip portion to shield an electromagnetic wave. The electromagnetic wave shield is formed by coating a conductive adhesive on a film with a metal film having an insulating layer and a conductive layer. The metal in the film with a metal film is copper or silver.
In recent years, mobile communication devices require large-capacity signal processing in order to realize high-speed internet and the like. Therefore, in order to process such a large-capacity signal, the signal processing of the semiconductor element is also performed at high speed, and electromagnetic wave noise is generated from the semiconductor element and the signal line in a large amount.
These electromagnetic wave noises interfere with an antenna component incorporated in the mobile communication device, and cause malfunction. Therefore, in order to shield electromagnetic wave noise associated with the increase in speed, a shielding film having more excellent shielding characteristics is required. In terms of shielding performance, the kind of the shielding material and the thickness of the shielding material are the dominant factors, and silver and copper having high electric conductivity and magnetic permeability are preferable, and a thick metal layer is preferable. In practice, in order to shield signals of frequencies of the 1GHz band, the resistance value of the metal layer needs to be 500m Ω/m 2 The resistance value below, for example, in the case of copper, needs to be 0.08 μm or more in thickness. On the other hand, the shield material has various shapes such as a semiconductor chip and a case, and shape-following property is required for bonding the shield film without a gap. If the metal layer and the film are thick, wrinkles are generated at the time of bonding and the shape cannot be followed, which is not preferable. Therefore, an electromagnetic wave shielding film is proposed which requires a thickness of 0.08 to 2.0 μm for the metal layer and a thickness of 4 to 75 μm for the film (for example, patent document 2).
Copper is used as a wiring material for a circuit board because of its low resistance, and is an indispensable material for an electromagnetic wave shielding material having high shielding performance because the thickness of the wiring material can be increased at a lower cost than silver. The copper vapor-deposited metallized film is produced by depositing copper of a target thickness on a resin film by a plating method or a vapor deposition method (including a sputtering method).
However, since copper is likely to undergo surface oxidation, surface oxidation of the metallized film occurs during the period from the production to the post-treatment process. Even if the circuit board is bonded with an adhesive while the surface oxide film remains, the surface oxide film may peel off at the interface. In addition, when plating by the semi-additive method is performed, copper of the metallized film is used as a seed layer, but when surface oxidation occurs, the resistance value increases, current supply becomes unstable, and the film thickness becomes uneven. The cleaning step using an acidic solution is effective for removing the surface oxide layer, but since copper is etched in the cleaning step, if the copper film is a thin film having a thickness of less than 1 μm, the film thickness may be greatly reduced or eliminated. In order to prevent this, a rust inhibitor treatment containing a benzoxazole compound as a main component is generally performed (for example, patent document 3).
However, if the rust inhibitor remains on the surface of the copper film, it causes interfacial peeling. Further, in the acid cleaning step for removing the rust inhibitor, the copper surface is etched, and therefore, it is not suitable for a thin film.
In order to solve this problem, it has been studied to provide a copper surface with another metal layer to obtain rust prevention performance (for example, patent documents 4 and 5).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007 and 24645
Patent document 2: japanese patent laid-open publication No. 2011-35213
Patent document 3: japanese laid-open patent publication No. 5-28835
Patent document 4: japanese patent laid-open publication No. 2016-153214
Patent document 5: japanese patent No. 4463442
Disclosure of Invention
Problems to be solved by the invention
However, many metals used for a rust-preventive layer have a dense oxide film formed on the surface thereof and a high resistivity, and when the thickness thereof is increased, the surface resistance increases, etching is inhibited by the dense metal oxide film, and a residue is generated, which may cause a pattern formation failure. Further, there are cases where: the metal layer used in the rust-preventive layer is oxidized, and if the metal layer changes into a relatively transparent oxide film with lost metallic luster, the color of the base copper can be seen, the metallic luster of the initial rust-preventive layer changes from the color tone, and the color change is judged to be abnormal.
In view of the above circumstances, an object of the present invention is to provide a metallized film that shows little change in resistance and chromaticity before and after a moisture resistance test.
Means for solving the problems
As a result of intensive studies in view of the above-described problems, the inventors of the present application have obtained a metallized film in which the change in resistance and chromaticity is small before and after the moisture resistance test is performed by setting the thickness of the titanium layer to an appropriate thickness, and a method for producing the metallized film.
That is, the present invention relates to a metallized film having a copper layer and a rust-preventive layer on at least one surface of the film in this order from the film side, wherein the rust-preventive layer contains at least one selected from the group consisting of metallic titanium, titanium oxide, and a mixture thereof, and the metallized film has a surface resistance change rate of 20% or less after 3 days in an 85 ℃ RH environment and a color difference Δ E of 6.5 or less after 3 days in the environment.
The present invention also relates to a method for producing a metallized film, wherein the copper layer and the rust preventive layer are formed by a vacuum deposition method or a sputtering method.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a metallized film having little change in resistance and chromaticity before and after the moisture resistance test is performed, and a method for producing the same can be obtained.
Drawings
FIG. 1 is a schematic cross-sectional view of a metallized film according to the present invention.
FIG. 2 is a schematic cross-sectional view of a metallized film according to the present invention.
Detailed Description
The present invention will be described in detail below.
< metallized film >
A preferred embodiment of the present invention is a metallized film having a copper layer and a rust-preventive layer on at least one surface of the film in this order from the film side, wherein the rust-preventive layer contains at least one selected from the group consisting of metallic titanium, titanium oxide, and a mixture thereof, the metallized film has a surface resistance change rate of 20% or less after 3 days in an 85% RH environment at 85 ℃ and a color difference Δ E of 6.5 or less after 3 days in the above environment. Further, a more preferable embodiment is the following embodiment: the metallized film has a copper layer on at least one side of the film and a rust preventive layer comprising metallic titanium, titanium oxide or a mixture thereof (fig. 1). As such, it is more preferable that the rust preventive layer is formed of metallic titanium, titanium oxide, or a mixture thereof.
< copper layer >
The copper layer according to the present invention is an aggregate of copper layers in which 1 or 2 or more layers containing copper as a main component are laminated. The main component means more than 80 atomic% when the whole layer is 100 atomic%.
The thickness of the copper layer in the present invention is preferably 0.05 μm to 3.0 μm, and more preferably 0.2 μm to 1.5 μm.
In the case of using the copper layer of 0.05 μm or more for the electromagnetic wave shielding material, the shielding performance is obtained, and the electromagnetic wave shielding performance is further improved in the case of 0.2 μm or more. In the case of a copper layer having a thickness of 0.1 μm or more, the conductivity can be secured when the plating treatment is performed by the semi-additive method, and the conductivity can be secured at a thickness of 0.2 μm or more for the purpose of forming an electronic circuit. On the other hand, in order to form a fine pattern on a printed circuit board by the semi-additive method, the copper layer needs to be thin to some extent, and considering the limitation of cost for forming the copper layer, it is desirable that the thickness of the copper layer is preferably 3.0 μm or less, more preferably 1.5 μm or less.
Examples of the vacuum deposition method include an induction heating deposition method, a resistance heating deposition method, a laser beam deposition method, and an electron beam deposition method. Any vapor deposition method can be used, and the electron beam vapor deposition method is suitably used from the viewpoint of having a high film formation rate. In the vapor deposition, the film may be vapor deposited while being cooled so that the temperature does not increase.
< anti-rust coating >
With respect to the rust preventive layer in the present invention, it is preferable that the rust preventive layer contains at least one selected from the group consisting of metallic titanium, titanium oxide, and a mixture thereof, and it is further preferable that the rust preventive layer is formed of metallic titanium, titanium oxide, or a mixture thereof.
The rust-preventive layer is preferably formed on the copper layer on at least one side of the film by a sputtering method among physical vapor deposition methods, and among these, vapor deposition using a target containing metallic titanium as a main component is preferable. The main component is more than 80 atomic% when the entire target is 100 atomic%. That is, it is preferable that titanium is contained in an amount of more than 80 at% out of 100 at% of the metal elements contained in the above rust preventive layer. In the vapor deposition, the film may be cooled and vapor deposited so that the temperature does not increase.
After the rust-proof layer is formed, the titanium oxide reacts with the atmosphere to oxidize a part of the metallic titanium, thereby forming titanium oxide having a high rust-proof effect. Since oxidation inside is suppressed by the titanium oxide film, layers having different oxygen concentrations are formed in the depth direction, and as a result, the rust-preventive layer as a whole becomes a mixture of metallic titanium and titanium oxide. When the rust-preventive layer is thick, titanium oxide exists on the surface layer and metallic titanium exists in a region away from the surface layer, and when the rust-preventive layer is thin, titanium oxide occupies a large part of the entire layer.
The above-mentioned rust preventive layer functions to protect the underlying copper layer. When the resistance change rate after the moisture resistance test is high, the copper layer is corroded, which is not preferable. Therefore, the resistance change rate is preferably 20% or less. From the viewpoint of the rate of change in resistance, the thicker the rust inhibitive layer thickness is, the better the color difference Δ E isIn view of the thinner film thickness, the smaller the change in the color difference Δ E is, which is preferable. The color difference Delta E is obtained by arranging a colorimeter from the side of the rust-proof layer by L ＊ a ＊ b ＊ The color is a value obtained by measuring reflected light including regular reflected light and calculating the value using the following formula. When the color difference Δ E is 6.5 or less, it is determined that there is no color difference as an allowable difference.
[ mathematical formula 1]
Measured value (L) before humidity resistance test at 85 ℃ under 85% RH atmosphere 0 ，a 0 ，b 0 )
Measured values (L, a, b) after a humidity resistance test at 85 ℃ under an atmosphere of 85% RH.
The thickness of the rust-preventive layer in the present invention is preferably 2nm or more and 8nm or less, more preferably 3nm or more and 5nm or less, and further preferably 3nm or more and 4nm or less. When the thickness of the rust-preventive layer is 2nm or more and 8nm or less, the surface resistance change rate can be more easily made 20% or less and the color difference Δ E can be more easily made 6.5 or less even after 3 days in an environment of 85 ℃ and 85% RH. Further, in the case where the thickness of the rust-preventive layer is 3nm or more and 5nm or less, it is possible to more easily satisfy the condition that the surface resistance change rate is 20% or less and the color difference Δ E is 6.5 or less even after 7 days in an environment of 85 ℃ and 85% RH. Further, in the case where the thickness of the rust preventive layer is 3nm or more and 4nm or less, it is possible to more easily satisfy the surface resistance change rate of 20% or less and the color difference Δ E of 6.5 or less even after 28 days in an environment of 85 ℃ and 85% RH.
When the copper film formed by vacuum deposition or sputtering is exposed to the atmosphere, a copper oxide film is formed on the surface of the copper film. Since CuO in the copper oxide film is a needle-like structure rather than a dense film, it is difficult to form a uniform and dense rust-preventive layer if a titanium film is formed on CuO, and the rust-preventive effect is weak, and therefore, it is preferable that a copper layer formed in a vacuum is not exposed to the atmosphere in view of improvement of the rust-preventive effect in sputtering of a rust-preventive layer using titanium.
On the other hand, in the production of a metallized film, it is sometimes difficult to form a titanium film as a rust-preventive layer on a copper film without exposing the film to the atmosphere due to the restrictions on the structure of the production apparatus and the film forming performance. In view of productivity and manufacturing cost, it is preferable to perform manufacturing in 1 line in which formation of a copper film by vacuum deposition and formation of a titanium film as a rust-preventive layer are continuously performed without opening the atmosphere, but if exposure of the copper film formed by vacuum deposition or sputtering to the atmosphere is allowed, the manufacturing apparatus and manufacturing process can be simplified, and a metallized film can be efficiently obtained in terms of time and energy. In order to obtain a metallized film efficiently and to optimize the rust-preventive effect, a method of manufacturing a metallized film may be employed in which a copper layer is vapor-deposited, then the atmosphere is opened, then copper sputtering is performed again in vacuum, and then titanium sputtering is continuously performed without opening the atmosphere.
If only the rust prevention effect is considered, the re-sputtered metal may be increased in thickness by nickel, chromium, or titanium instead of copper before titanium sputtering is performed on the surface of the copper film opened through the atmosphere.
In the case of copper sputtering performed on a copper surface opened through the atmosphere, the thickness of sputtered copper is preferably 1nm or more. By setting Cu sputtering to 1nm or more, the brittle copper oxide present on the copper surface exposed to the atmosphere is also removed, and a copper film formed by sputtering is formed thereon. Further, by continuously performing titanium sputtering without opening the atmosphere of the sputtered copper film, a stable rust-preventive layer can be obtained.
The thickness of the rust-preventive layer in the present invention may be defined by the reflectance of light immediately after film formation. When the reflectance of the metal layer of the rust-preventive layer at a wavelength of 800nm is 82% or more and the ratio R800/R300 of the reflectance R800 at a wavelength of 800nm to the reflectance R300 at a wavelength of 300nm is 5.0 or more and 10.0 or less, the surface resistance change rate is 20% or less and the color difference Delta E is 6.5 or less can be satisfied even after 3 days in an 85% RH atmosphere at 85 ℃. Since the rust-proof layer immediately after film formation is thin, it is difficult to measure the thickness directly, but by checking the reflectance of light, the optimum value of the rust-proof layer thickness can be easily checked.
< membrane >
The film used in the present invention is a film formed by molding a polymer such as a synthetic resin into a thin film.
As the film suitably used in the present invention, for example, a polyester film can be used, and among the polyester films, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyimide film, a polyphenylene sulfide film, and a polypropylene film can be used. Among them, a polyethylene terephthalate film is more preferably used. These films may be used alone or as a composite film. In addition, a film in which a resin, an adhesive, or the like is coated on the film surface may also be used.
The thickness of the film is preferably 1 μm to 200 μm. The appropriate thickness of the film varies depending on the application, and for example, in the case of an electromagnetic wave shield used for a very fine coaxial cable, if the thickness of the film is less than 1 μm, the film may be deformed or broken when wound around the very fine coaxial cable. When the diameter exceeds 10 μm, the extra-fine coaxial cable may have a large diameter and poor flexibility. As another application, when the film of the electromagnetic wave shielding gasket product used for measures against EMI (electromagnetic interference) is less than 10 μm, the film may be deformed or broken by stress applied at the time of gasket production. If the thickness exceeds 50 μm, the gasket itself becomes thick, which is not suitable for space saving, and the influence of the rigidity of the film becomes large, and the flexibility of the gasket itself is lost. In addition to the above, when the metallized film is treated with a printed substrate or a touch sensor, it is generally preferable that the film has a thickness of 50 μm or more and 200 μm or less, since the film can be held as a substrate and can satisfy electrical characteristics.
< buffer layer >
A buffer layer may also be provided between the film and the copper layer of the metallized film of the present invention. By providing the buffer layer, the adhesion force between the film and the copper layer can be expected to be improved. In the case of a polyimide film, the buffer layer also functions as a film for preventing diffusion of copper into the film, and it is expected that a decrease in adhesion force due to copper diffusion can be prevented. As the buffer layer, a metal layer is preferably formed on the film by a sputtering method. The sputtering method can reduce the thickness of the buffer layer, and is most suitable for an electromagnetic wave shield application requiring further reduction in thickness.
The buffer layer is preferably a metal layer containing at least one selected from the group consisting of copper, nickel, titanium, nichrome, and chromium. When the film is made of a material that diffuses copper, such as polyimide, the adhesion force can be prevented from being reduced by selecting from nickel, titanium, chromium, nichrome, and the like, which can suppress the diffusion of copper into the film. At this time, it should be noted that it is important to form a copper layer thereon while maintaining a state in which the surface of a metal such as nickel, titanium, chromium, and nichrome selected as a buffer layer is not oxidized. Specifically, it is important to form a copper film in a state where a metal layer is formed as a buffer layer by sputtering and then vacuum is maintained without opening the atmosphere. When a metal surface of nickel, titanium, chromium, nichrome or the like selected as the buffer layer is oxidized, a stable metal oxide film is formed, and metal bonding with an interface of a copper layer formed thereon becomes difficult, and adhesion force cannot be secured, and the copper layer may be peeled off from the buffer layer. Therefore, it is important that nickel, titanium, chromium, nichrome, or the like selected as the buffer layer is not oxidized.
The thickness of the buffer layer is preferably 5nm to 40nm, more preferably 10nm to 20 nm. If the thickness is less than 5nm, a sufficient adhesive force may not be obtained. On the other hand, if the thickness exceeds 40nm, the average crystal grain size of the buffer layer formed by sputtering becomes large, and depending on the kind of metal, the copper layer formed thereon is affected by the size of the crystal grain size of the buffer layer, and the average crystal grain size of the copper layer also becomes large, and control may become difficult. In the case of metals other than copper, if the thickness exceeds 40nm, etching removal by etching of copper becomes difficult, and 2-stage etching, in which an etching step dedicated to buffer metals is added after the copper etching step, may be necessary.
Examples
The present invention will be described below based on examples. The present invention is not limited to these embodiments, and modifications and changes can be made to these embodiments based on the gist of the present invention, and these embodiments are not excluded from the scope of the present invention.
(magnetron sputtering)
A film was set in a batch vacuum deposition apparatus (EBH-800 made by ULVAC), and a target having a size of 50mm × 550mm was used, and the film was adjusted in an argon atmosphere to a vacuum degree of 5 × 10 -1 Pa or less, and continuously applying DC power for a certain period of time until the metal film thickness reaches a predetermined value.
Alternatively, a film was set in a roll-to-roll vacuum deposition apparatus (EWC-060, manufactured by ULVAC), and a target having a size of 70mm × 550mm was used, and the film was adjusted in an argon atmosphere to a vacuum degree of 1 × 10 -2 Pa or less, and applying DC power to form a metal layer.
Unless otherwise specified, sputtering and vacuum deposition are continuously performed so that the buffer layer, the copper layer, and the rust-preventive layer are not in contact with the atmosphere.
(vacuum deposition)
A film was provided in an intermittent vacuum deposition apparatus (EBH-800 made by ULVAC), copper was placed on a deposition boat in an amount corresponding to a target thickness, and then the boat was evacuated until the vacuum degree reached 9.0X 10 -3 And heating the evaporation boat until Pa is lower than Pa, and performing vacuum evaporation to form a copper layer.
Alternatively, a film is provided in a roll-to-roll vacuum deposition apparatus (EWC-060, manufactured by ULVAC), and vacuum deposition is performed under conditions of a transport speed and an output power at which the thickness of the copper layer reaches a predetermined value, thereby forming a copper layer.
(moisture resistance test)
The metallized film was cut into a size of about 300mm × about 80mm, and attached to a plastic plate, and then the metallized film was placed downward so that water droplets did not adhere thereto, and the plate was placed in a constant temperature and humidity chamber (THC-120, manufactured by IMV) at 85% RH for a predetermined time.
(measurement of surface resistance and calculation of resistance Change Rate)
The metallized film was cut into a size of about 300mm × about 80mm, and the surface resistance of the side of the rust-preventive layer (the copper layer side when no rust-preventive layer was provided) at 10 points in the surface was measured by a four-terminal method using a simple low resistivity meter ("Loresta (registered trademark)" EP MCP-T360 manufactured by Mitsubishi Chemical analysis co.
Surface resistance R before test according to moisture resistance 0 And a surface resistance R after a humidity resistance test at 85 ℃ and 85% RH, and the change rate Δ R was calculated by using the following formula. The calculated change rate was judged to be good if it was 20% or less, and judged to be poor if it exceeded 20%.
ΔR＝(R-R 0 )/R 0 。
(thickness of antirust layer)
A sample having only a rust preventive layer deposited on a film was prepared, and the transmittance at a wavelength of 555nm was measured by a transmittance meter (portable black-white transmittance meter Ihac-T5, manufactured by Jingyuan electronics industries Co., Ltd.). The metal thickness calculation was performed using Lambert-Beer (Lambert-Beer) rule, substituting into the following equation. The extinction coefficient used for the calculation was 2.56.
[ mathematical formula 2]
I: the quantity of light after passing through the film
I 0 : initial light quantity
k: extinction coefficient
Z: film thickness (nm)
λ: wavelength (nm).
(measurement of color intensity and calculation of color difference. DELTA.E)
The surface color was measured with a color difference meter (CM-2500 d manufactured by Konica Minolta). The measurement was carried out under conditions including regular reflection light (incident angle 8 DEG, reflection angle 8 DEG), and L was used ＊ a ＊ b ＊ The color system is used as the color system.
The measurement results were substituted into the following values to calculate the color difference Δ E.
[ mathematical formula 3]
Measured value (L) before humidity resistance test at 85 ℃ under 85% RH atmosphere 0 ，a 0 ，b 0 )
Measured values (L, a, b) after a humidity resistance test at 85 ℃ under an atmosphere of 85% RH
When the color difference Δ E is 6.5 or less, no color change is determined to be good, and when it exceeds 6.5, a color change is large, and thus determined to be x.
(measurement of reflectance of Metal layer)
The reflectance of the metal layer was measured under the following conditions using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by Nippon spectral Co. From the obtained spectral data, the reflectance at a wavelength of 800nm was designated as R800, and the reflectance at a wavelength of 300nm was designated as R300, and the reflectance ratio of R800/R300 was calculated.
Measurement mode: reflectance Pattern (5 degree)
Measurement wavelength range: 300 to 1,000nm
Data acquisition interval: 0.5nm
Scanning speed: 1,000nm/min
UV/Vis bandwidth: 5.0nm
NIR bandwidth: 20.0 nm.
(measurement of electric field Shielding Performance)
The electric field shielding performance (dB) at 1GHz was measured by the KEC method using a microwave/millimeter wave band evaluation system E5071C ENA network analyzer (manufactured by Agilent). The upper limit of the measurement is a measurement result obtained by sandwiching a copper plate having a thickness of 3mm between the measurement limits. In addition, since it is considered that there is almost no electromagnetic wave shielding effect when the measured value of the electric field shielding performance is 10dB or less, the measured value of the electric field shielding performance of 10dB or more is required as the electromagnetic wave shielding material. Since the change of the electric field shielding effect E0/Ei (Ei: incident electric field (V/m), E0: transmission electric field (V/m)) by about 20% corresponds to a 2dB change in the measured value of the electric field shielding performance, if the change is within 2.0dB from the initial measured value, it is determined as "o" as no problem, and if the change exceeds 2.0dB, it is determined that the initial performance cannot be maintained, and it is determined as "x".
(example 1)
As the buffer layer, a biaxially oriented polyethylene terephthalate film (manufactured by Toray corporation, the "Lumiror (registered trademark)" type: F68) in which titanium was deposited in a thickness of 5nm to a thickness of 16 μm was formed by magnetron sputtering using a batch vacuum deposition apparatus (EBH-800 manufactured by ULVAC) was used. As a condition, 5.0kW was used for the sputtering output power using a DC power supply. The sputtering target used was a 99.9 wt% titanium sputtering target. Then, copper was vacuum-evaporated to a thickness of 100nm by a vacuum evaporation method. The evaporation used a raw material of 99.9 wt% copper. Then, titanium was deposited by magnetron sputtering to a thickness of 2nm to form a rust-preventive layer. As a condition, 2.0kW was used for the sputtering output power using a DC power supply. The sputtering target used was a 99.9 wt% titanium sputtering target.
The metallized film thus produced had a surface resistance R before a humidity resistance test at 85 ℃ under an atmosphere of 85% RH 0 The measurement was carried out, and the result was 0.252. omega./□. Further, surface color (L) before humidity resistance test at 85 ℃ under 85% RH atmosphere 0 ，a 0 ，b 0 ) The results of the measurements of (1) were (88.19, 13.85, 16.79). The metal layer on the rust-proof layer side at a wavelength of 800nm had a reflectance R800 of 91% and a ratio R800/R300 of 5.0. Further, the electric field shielding performance was measured, and the result was 54.6 dB.
Then, after the humidity resistance test was performed for 3 days, 7 days, and 28 days at 85 ℃ and 85% RH, the surface resistance, chromaticity, and electric field shielding performance were measured for each sample, and the determination was made based on the results.
The surface resistance 3 days after the moisture resistance test was 0.251. omega./□, and the change rate was calculated to be-0.4% and judged as O. On the other hand, the measurement results of the surface color (L, a, b) after the humidity resistance test at 85 ℃ under 85% RH were (84.87, 16.37, 21.58), and the color difference Δ E was calculated to be 6.36 and judged as ∘. The electric field shielding performance measurement result was 54.1dB, and the change was-0.5 dB, and the result was determined to be O.
The surface resistance 7 days after the moisture resistance test was 0.268. omega./□, and the change rate was calculated to be 6.3% and judged as O. On the other hand, the measurement results of the surface chromaticities (L, a, b) after the humidity resistance test at 85 ℃ under 85% RH atmosphere were (69.85, 17.86, 24.10), and the color difference Δ E was calculated to be 20.15 and judged to be x. The electric field shielding performance measurement result was 55.6dB, and the change was 1.0dB, which was determined to be o.
The surface resistance after 28 days of the moisture resistance test was 0.471. omega./□, and the calculated change rate was 87.0% and judged as X. On the other hand, the measurement results of the surface color (L, a, b) after the humidity resistance test at 85 ℃ under 85% RH atmosphere were (77.74, 15.28, 22.49), and the color difference Δ E was calculated to be 12.00 and judged as X. Further, the electric field shielding performance measurement result was 47.8dB, the change was-6.8 dB, and the result was judged to be x.
(examples 2 and 12)
A metallized film was produced and evaluated in the same manner as in example 1, except that the thicknesses of the substrate and the rust-preventive layer were set as shown in table 1 and the sputtering output of the rust-preventive layer was set to 3.1 kW. The results are shown in tables 1 and 2.
(example 3)
A metallized film was produced and evaluated in the same manner as in example 1, except that the thickness of the rust-preventive layer was set as shown in table 1 and the sputtering output of the rust-preventive layer was set to 4.2 kW. The results are shown in tables 1 and 2.
(examples 4 to 7)
A metallized film was produced and evaluated in the same manner as in example 1, except that the thickness of the rust-preventive layer was set as shown in table 1 and the sputtering output of the rust-preventive layer was set to 5.0 kW. The results are shown in tables 1 and 2.
(example 8)
As the buffer layer, a biaxially oriented polyethylene terephthalate film (manufactured by Toray corporation, the "Lumiror (registered trademark)" type: F68) in which titanium was deposited in a thickness of 5nm to a thickness of 16 μm was formed by magnetron sputtering using a batch vacuum deposition apparatus (EBH-800 manufactured by ULVAC) was used. As a condition, 5.0kW was used for the sputtering output power using a DC power supply. Then, copper was vacuum-evaporated to a thickness of 100nm by a vacuum evaporation method. Then, the substrate was left to stand for 8 hours with the atmosphere open, and titanium was deposited by a magnetron sputtering method to a thickness of 5nm using a batch vacuum deposition apparatus (EBH-800, manufactured by ULVAC) to form a rust-proof layer. As a condition, 5.0kW was used for the sputtering output power using a DC power supply. The evaluation results of the produced film are shown in tables 1 and 2.
(example 9)
As the buffer layer, a biaxially oriented polyethylene terephthalate film (manufactured by Toray corporation, the "Lumiror (registered trademark)" type: F68) in which titanium was deposited in a thickness of 5nm to a thickness of 16 μm was formed by magnetron sputtering using a batch vacuum deposition apparatus (EBH-800 manufactured by ULVAC) was used. As a condition, 5.0kW was used as the sputtering output power using a DC power supply. Then, copper was vacuum-evaporated to a thickness of 100nm by a vacuum evaporation method. After leaving for 8 hours with the atmosphere open, copper was deposited to a thickness of 1nm by magnetron sputtering using a batch vacuum deposition apparatus (EBH-800, ULVAC), and titanium was deposited to a thickness of 5nm by magnetron sputtering without opening the atmosphere to form a rust-preventive layer. As conditions, the same DC power source was used for both copper and titanium in terms of sputtering output, whereas 2.0kW was used for copper sputtering and 5.0kW was used for titanium sputtering. The evaluation results of the produced film are shown in tables 1 and 2.
(example 10)
A metallized film was produced and evaluated in the same manner as in example 2, except that no buffer layer was provided. The results are shown in tables 1 and 2.
(example 11)
Metallized films were produced and evaluated in the same manner as in example 2, except that the thicknesses of the substrate and the rust-preventive layer were set as shown in table 1 and copper was vacuum-deposited at a thickness of 1000 nm. The results are shown in tables 1 and 2.
Comparative example 1
As the buffer layer, a biaxially oriented polyethylene terephthalate film (manufactured by Toray corporation, the "Lumiror (registered trademark)" type: F68) in which titanium was deposited in a thickness of 5nm to a thickness of 16 μm was formed by magnetron sputtering using a batch vacuum deposition apparatus (EBH-800 manufactured by ULVAC) was used. As a condition, 5.0kW was used for the sputtering output power using a DC power supply. Then, copper was vacuum-evaporated to a thickness of 100nm by a vacuum evaporation method. Then, no rust preventive layer was formed.
The metallized film thus produced had a surface resistance R before a humidity resistance test at 85 ℃ under an atmosphere of 85% RH 0 The measurement was carried out, and the result was 0.213. omega./□. Further, surface color (L) before humidity resistance test at 85 ℃ under 85% RH atmosphere 0 ，a 0 ，b 0 ) The results of the measurements of (8) were (88.47, 13.29, 16.18). In addition, the reflectance R800 of the metal layer at a wavelength of 800nm on the copper layer side was 94%, and the ratio R800/R300 was 3.5. Further, the electric field shielding performance was measured, and the result was 54.5 dB.
Then, after a moisture resistance test was performed for 3 days, 7 days, and 28 days at 85 ℃ and 85% RH, the surface resistance, chromaticity, and electric field shielding performance were measured for each sample, and the results were used to determine the resistance.
The surface resistance 3 days after the moisture resistance test was 0.723. omega./□, and the calculated change rate was 239%, and the test was judged as X. On the other hand, the measurement results of the surface color (L, a, b) after the humidity resistance test at 85 ℃ under 85% RH atmosphere were (57.43, 10.89, 21.44), the color difference Δ E was calculated, and the result was 31.57 and was judged as X. Further, the electric field shielding performance measurement result was 44.0dB, the change was-10.5 dB, and the result was judged to be X.
The surface resistance after 7 days of the moisture resistance test was judged as X because it was not measured beyond the range of the resistivity meter. On the other hand, the measurement results of the surface color (L, a, b) after the humidity resistance test at 85 ℃ under 85% RH atmosphere were (50.65, 6.80, 20.03), and the color difference Δ E was calculated to be 38.57 and judged as X. In addition, when the electric field shielding performance is 10dB or less, the measured value fluctuates and the value is difficult to be determined, but since the electric field shielding effect of 10dB or less is almost no, it is regarded as 0 dB. The variance was set to-54.5 dB and the decision was set to X.
The surface resistance after 28 days of the moisture resistance test was judged to be X, because it was not measured beyond the range of the resistivity meter. On the other hand, the surface color (L, a, b) after the humidity resistance test at 85 ℃ under 85% RH was measured, but the metal film was peeled off by corrosion and could not be measured, and was judged as X. In addition, when the electric field shielding performance is 10dB or less, the measured value fluctuates and the value is difficult to be determined, but since the electric field shielding effect of 10dB or less is almost no, it is regarded as 0 dB. The variance was set to-54.5 dB and the decision was set to X.
Comparative examples 2 and 3
A metallized film was produced and evaluated in the same manner as in example 1, except that the thickness of the rust-preventive layer was set as described in table 1. The results are shown in tables 1 and 2. In comparative examples 2 and 3, the surface resistance after 7 days and 28 days after the moisture resistance test could not be measured beyond the range of the resistivity meter. Similarly, when the electric field shielding performance measurement result is 10dB or less, the measurement value fluctuates and the value is difficult to be determined, but since the electric field shielding effect of 10dB or less is almost no, it is regarded as 0 dB. Further, the metal film was peeled off by corrosion, and the surface color after 28 days after the humidity resistance test could not be measured.
Comparative example 4
As the buffer layer, a biaxially oriented polyethylene terephthalate film (manufactured by Toray corporation, the "Lumiror (registered trademark)" type: F68) in which titanium was deposited in a thickness of 5nm to a thickness of 16 μm was formed by magnetron sputtering using a batch vacuum deposition apparatus (EBH-800 manufactured by ULVAC) was used. As a condition, 5.0kW was used for the sputtering output power using a DC power supply. Then, copper was vacuum-evaporated to a thickness of 100nm by a vacuum evaporation method. Then, titanium was deposited by magnetron sputtering to a thickness of 10nm to form a rust-preventive layer. As a condition, 5.0kW was used for the sputtering output power using a DC power supply. The evaluation results of the produced film are shown in tables 1 and 2.
Comparative example 5
Copper was vacuum-deposited to a thickness of 16 μm by a vacuum deposition method using a roll-type vacuum deposition apparatus (EWC-060, manufactured by ULVAC) to form a biaxially oriented polyethylene terephthalate film (F68, manufactured by Toray corporation, model "Lumiror (registered trademark)") having a thickness of 200 nm. Then, a 50-fold diluted solution of a benzotriazole-based rust inhibitor ("Pal C (japanese text: パル C)", manufactured by Tatsuta Electric Wire & Cable co., Ltd., "about 10% alcoholic solution of an about 2: 1 mixture of benzotriazole and a monoethanolamine salt thereof) in methanol was applied by a 200-mesh gravure coater, and dried at 70 ℃ to subject the surface to benzotriazole treatment. The evaluation results of the produced film are shown in tables 1 and 2.
[ Table 1]
[ Table 2]
Description of the reference numerals
1 film
2 buffer layer
3 copper layer
4 antirust layer
Claims (18)
1. A metallized film having a copper layer and a rust-preventive layer on at least one surface of the film in this order from the film side, wherein the rust-preventive layer contains at least one selected from the group consisting of metallic titanium, titanium oxide, and a mixture thereof, and the metallized film has a rate of change in surface resistance on the rust-preventive layer side of 20% or less after 3 days in an environment of 85 ℃ and 85% RH and a color difference [ Delta ] E of 6.5 or less after 3 days in the environment.
2. The metallized film of claim 1, wherein the rust preventative layer is formed from metallic titanium, titanium oxide, or mixtures thereof.
3. The metallized film according to claim 1 or 2, wherein the thickness of the rust preventive layer is 2nm or more and 8nm or less.
4. The metallized film according to any one of claims 1 to 3, wherein a reflectance at a wavelength of 800nm on the rust-preventive layer side is 82% or more,
the ratio R800/R300 of the reflectance R800 at a wavelength of 800nm to the reflectance R300 at a wavelength of 300nm is 5.0 to 10.0.
5. The metallized film according to any one of claims 1 to 4, wherein a surface resistance change rate on the rust-preventive layer side after 7 days in an environment of 85 ℃ and 85% RH is 20% or less, and a color difference Δ E after 7 days in the environment is 6.5 or less.
6. The metallized film according to any one of claims 1 to 5, wherein the rust-preventive layer has a thickness of 3nm or more and 5nm or less.
7. The metallized film according to any one of claims 1 to 6, wherein a surface resistance change rate on the rust-preventive layer side after 28 days in an environment of 85 ℃ and 85% RH is 20% or less, and a color difference Δ E after 28 days in the environment is 6.5 or less.
8. The metallized film according to any one of claims 1 to 7, wherein the rust-preventive layer has a thickness of 3nm or more and 4nm or less.
9. The metallized film of any one of claims 1 to 8, wherein there is a buffer layer between the copper layer and the film.
10. The metallized film of claim 9, wherein the buffer layer comprises at least one selected from the group consisting of copper, titanium, nickel-chromium alloy, and chromium.
11. The metallized film according to any one of claims 1 to 10, wherein the film thickness of the copper layer is 0.05 μm or more and 3.0 μm or less.
12. The metallized film according to any one of claims 1 to 11, wherein the film is at least one selected from the group consisting of polyester, polyimide, polyphenylene sulfide, and polypropylene.
13. The metallized film of any one of claims 1 to 12, wherein the film has a thickness of 1 μ ι η or more and 200 μ ι η or less.
14. The metallized film according to any one of claims 1 to 13, wherein the film has a thickness of 1 μm or more and 10 μm or less.
15. The metallized film of any one of claims 1 to 13, wherein the film has a thickness of 10 μ ι η or more and 50 μ ι η or less.
16. The metallized film of any one of claims 1 to 13, wherein the film has a thickness of 50 μ ι η or more and 200 μ ι η or less.
17. The method for producing a metallized film according to any one of claims 1 to 16, wherein the copper layer and the rust-preventive layer are formed by a vacuum evaporation method or a sputtering method.
18. The method of manufacturing a metallized film according to claim 17, wherein after the copper layer is evaporated, an atmosphere is opened, and then, after the copper sputtering is performed again in vacuum, the titanium sputtering is continuously performed without opening the atmosphere.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-068045 | 2020-04-06 | ||
| JP2020068045 | 2020-04-06 | ||
| PCT/JP2021/014449 WO2021206039A1 (en) | 2020-04-06 | 2021-04-05 | Metallized film and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| CN114981077A true CN114981077A (en) | 2022-08-30 |
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| CN202180010047.4A Pending CN114981077A (en) | 2020-04-06 | 2021-04-05 | Metallized film and method for manufacturing same |
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| Country | Link |
|---|---|
| JP (1) | JPWO2021206039A1 (en) |
| KR (1) | KR20220163345A (en) |
| CN (1) | CN114981077A (en) |
| WO (1) | WO2021206039A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2021206039A1 (en) | 2021-10-14 |
| WO2021206039A1 (en) | 2021-10-14 |
| KR20220163345A (en) | 2022-12-09 |
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