WO2010032783A1 - Revêtement interférentiel optique - Google Patents

Revêtement interférentiel optique Download PDF

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Publication number
WO2010032783A1
WO2010032783A1 PCT/JP2009/066249 JP2009066249W WO2010032783A1 WO 2010032783 A1 WO2010032783 A1 WO 2010032783A1 JP 2009066249 W JP2009066249 W JP 2009066249W WO 2010032783 A1 WO2010032783 A1 WO 2010032783A1
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WO
WIPO (PCT)
Prior art keywords
thin film
layer
film
interference thin
refractive index
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Application number
PCT/JP2009/066249
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English (en)
Japanese (ja)
Inventor
一光 田中
信政 南部
太郎 北村
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株式会社ライク
株式会社タナカ技研
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Publication of WO2010032783A1 publication Critical patent/WO2010032783A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/285—Interference filters comprising deposited thin solid films
    • G02B5/287—Interference filters comprising deposited thin solid films comprising at least one layer of organic material

Definitions

  • the present invention relates to an optical interference thin film in which a unique reflected light for decoration can be obtained by a multilayer thin film laminated on the surface of an article.
  • Patent Document 1 High refractive index so that the concavo-convex structure is preserved up to the uppermost layer on the structural color body (Patent Document 1) whose color changes according to the observation direction due to the reflection / interference phenomenon or the ground surface having a fine concavo-convex structure
  • Patent Document 2 A structural color body (Patent Document 2) is known in which two types of optical thin films having a low refractive index are laminated and an exterior color in a limited wavelength band including a specific color is clearly observed.
  • Multilayer optical thin films used in these structural color bodies are based on the design principle of conventional optical interference thin films, assuming that the thin film layers to be laminated are sufficiently transparent.
  • a unique appearance color is obtained by utilizing wavelength selectivity according to the combination of the refractive index and the film thickness, such as a film or a color separation filter.
  • the structural color body of Patent Document 1 has a feature that the color tone changes when the observation direction is changed, and the structural color body of Patent Document 2 has a characteristic that clear reflected light in a specific wavelength band can be obtained.
  • An object of the present invention is to provide an optical interference thin film that can give a deep and unique hue as seen in lacquer coating to the appearance colors of various products and that can be easily manufactured industrially. is there.
  • the present invention pays attention to the fact that the unique shade of lacquer coating cannot be realized by ignoring the light absorption of the thin film.
  • a decorative effect having a unique color is obtained by utilizing a synergistic effect of the light interference phenomenon and the light absorption phenomenon by the thin film having a multilayer structure. Therefore, the optical interference thin film of the present invention has a film configuration in which an interference thin film layer in which at least two types of thin films having different refractive indexes n are laminated is formed on the base substrate side, and the surface side is covered with a transparent protective film.
  • the protective layer is intended to protect the interference thin film layer from mechanical shocks applied from the outside and changes in the surrounding environment, and is transparent with a refractive index n of 1.35 to 1.65 and a film thickness of 0.3 to 100 ⁇ m.
  • a membrane can be utilized.
  • the base substrate itself is a material with excellent adhesion, the optical interference thin film may be laminated on the surface of the base substrate. However, if the structure of the substrate surface itself is not suitable for thin film lamination, the substrate surface In order to improve adhesion, the optical interference thin film may be laminated after forming a metal layer.
  • At least one kind of thin film used for the interference thin film layer is required to have a refractive index n and an extinction coefficient k having significant values.
  • a titanium nitride film can be effectively used. it can.
  • a titanium nitride film is used as one interference thin film layer, it is easy to use a nitride film as the other thin film.
  • a silicon nitride film can be used preferably.
  • an interference thin film layer can be formed by alternately laminating these titanium nitride films and silicon nitride films.
  • an interference thin film layer can be obtained by using a thin film other than a nitride film
  • a metal film can also be used as a transparent thin film having absorption by appropriately adjusting the film thickness, and thus different metal films can be sequentially used. It is also possible to obtain the desired interference thin film layer by laminating the film or a combination with a dielectric film.
  • the optical interference thin film of the present invention not only can the reflected light from the object surface be appropriately colored by the synergistic effect of the interference action and the light absorption action of the optical thin film, but also the depth can be increased by the light absorption action of the thin film. It is possible to give a soothing shade of color and to obtain a unique decorative effect with a high-class feeling like lacquering.
  • a protective layer and a stain prevention layer durability against the use environment and resistance to mechanical impact can be improved, and stains such as fingerprints can be made inconspicuous and a high-quality decoration effect can be maintained.
  • the optical interference thin film of the present invention is used as a decorative coating 2, from the metal layer L 1 and the second thin film layer L 2 to the eighth thin film layer L 8 formed on the surface of the base substrate 3.
  • the interference thin film layer Ls composed of seven layers, and a ninth protective layer L9 laminated on the surface thereof.
  • the base substrate 3 is an exterior part of various products or components, and the material thereof may be an appropriate material such as metal, plastic, ceramic.
  • the metal layer L1 is a layer for covering the surface of the base substrate 3 so that the surface color of the base substrate 3 itself is not mixed with the unique reflected light obtained by the decorative coating 2, and aluminum (Al), silver (Ag), A near-colorless reflective color such as chromium (Cr) or nickel (Ni) is suitable, but a metal such as copper (Cu) or gold (Au) can be used as necessary. Further, depending on the material of the base substrate 3, adhesion may be a problem with the thin film laminated thereon. In such a case, the adhesion is improved by interposing these metal layers L ⁇ b> 1. Can do. Therefore, the metal layer L1 is omitted when the surface of the base substrate 3 is excellent in adhesion to the thin film and the surface color is of a level that does not affect the reflected light to be obtained by the decorative coating 2. Is also possible.
  • the metal layer L1 to the eighth thin film layer L8 can be efficiently formed by ion plating, and the protective layer L9 can be easily formed by coating. Further, the metal layer L1 can be formed by plating or painting in addition to PVD such as ion plating or vacuum deposition.
  • the film configuration of the decorative coating 2 is as shown in Table 1.
  • the refractive index n at the center wavelength ⁇ 0 is 0.83413
  • the extinction coefficient k is 5.63192.
  • Aluminum has high adhesion to various materials generally used for the base substrate 3, and also has excellent adhesion to the interference thin film layer Ls laminated thereon, and not only ion plating but also vacuum deposition and sputtering. However, it can be formed easily.
  • the aluminum thin film is not only used for the purpose of improving the adhesion, but also formed as an interference thin film layer Ls as one constituent layer having a refractive index n of 0.83413 at the center wavelength ⁇ 0 and an extinction coefficient k of 5.63192. Can also be used.
  • the interference thin film layers Ls from the second layer to the eighth layer are alternating layers of a titanium nitride film (TiN) having a refractive index n of 2.44582 and a silicon nitride film (SiN) having a refractive index n of 1.70199. It is configured. Since the titanium nitride films of the thin film layers L2, L4, L6, and L8 have an extinction coefficient k of 0.28458 and act as a light absorption film, the light passing through these titanium nitride films has a physical thickness. Decreases accordingly.
  • the interference thin film layer Ls gives a wavelength-dependent intensity modulation to the reflected light by an optical interference action determined by a combination of the refractive index n of the titanium nitride film and the silicon nitride film and the optical film thickness nD / ⁇ 0. .
  • the ninth protective layer L9 is a transparent fluororesin coating material layer, and its physical film thickness is set to 10 ⁇ m within the range of 0.3 to 100 ⁇ m.
  • Such spectral reflection characteristics provide intensity modulation that causes the interference thin film layer Ls to bias the peak of reflected light toward the long wavelength side, and the light absorption action of the titanium nitride film and the aluminum metal layer L1 is in the visible light range.
  • the reflected light in the shorter wavelength region than the center wavelength ⁇ 0 becomes 7 to 8% at most, and is buried in the red reflected light so that it is hardly noticeable.
  • the red reflected light thus obtained is not observed as surface reflection from the protective layer L9, but reflected light from the interface between the titanium nitride film and the silicon nitride film is observed through these nitride film and protective film L9. For this reason, the color tone has a deep hue as seen in lacquering.
  • the operation of the interference thin film layer Ls described above is not necessarily unique to the alternating layers of the titanium nitride film and the silicon nitride film.
  • at least two types of thin films having different refractive indexes n are alternately laminated, and the optical thickness is adjusted to give the reflected light a wavelength-dependent intensity modulation. At least one of them may have a light absorbing action.
  • a film, a dielectric film, or the like can be used as appropriate.
  • the interference thin film layer Ls is composed of a combination of a titanium nitride film and a silicon nitride film as in the above embodiment, nitrogen gas can be commonly used in the film formation process, so that the film formation conditions can be stabilized. This is advantageous in maintaining the film, and after the metal layer L1 is formed, the two kinds of thin films may be alternately stacked, so that the film forming operation can be made efficient. Furthermore, since the nitride films are stacked, stress between layers is less likely to occur, which is advantageous in preventing peeling failure.
  • the protective layer L9 protects the interference thin film layer Ls from mechanical shocks, and prevents the interference thin film layer Ls from being deteriorated or altered by changes in the surrounding environment. Since it has a low refractive index, it also has an effect of reducing surface reflection. In addition, the protective layer L9 substantially reduces the incident angle of external light to the interference thin film layer Ls as compared with the case where it directly enters from the atmosphere, and reduces the angle dependency of the spectral reflection characteristics peculiar to the multilayer interference thin film. To do. This makes it possible to obtain a stable reflected color with little change in color tone even when the observation angle is slightly changed.
  • the spectral reflection characteristics when an antireflection film is laminated on the surface are as shown by the broken line, and the reflected light on the short wavelength side is reduced as a whole because the amount of reflected light is reduced. It turns out that it is further suppressed.
  • a transparent coating material of silicon or Teflon (registered trademark) is preferably used, and the thickness is preferably in the range of 10 to 50 ⁇ m. These coating materials have the effect of making fingerprints and other dirt inconspicuous, and also have excellent wiping properties. When fingerprints are attached, they can be easily wiped after moistening the surface with a small amount of water or solvent. .
  • the film calculation was performed according to the same method to prepare samples for blue reflection, green reflection, and magenta reflection, and the obtained spectral reflection characteristics are shown in FIGS.
  • the broken line represents the characteristics of the laminated layers up to the protective layer
  • the solid line represents the characteristics of a layer obtained by further laminating a transparent coating material of silicon or Teflon (registered trademark) as an antireflection film. From these results, it can be seen that by changing the film configuration, the reflected light of the lacquered tone that is darkly sunk for various color tones can be obtained.
  • the ion plating apparatus used for the test film formation has a structure schematically shown in FIG.
  • a dome-shaped substrate holder 11 is provided in the vacuum chamber 10 so as to be rotatable around a vertical axis as shown in the figure, and the sample 12 shown in FIG.
  • argon gas is introduced as a discharge gas into the vacuum layer 10 to generate a plasma P of argon gas on the lower surface of the substrate holder 11.
  • nitrogen gas is introduced into the vacuum chamber 10 as a reaction gas, titanium particles are evaporated from an evaporation source 15 using an electron gun as indicated by an arrow 16, and accelerated ions are directed from the plasma gun 17 toward the substrate holder 11. Supply.
  • accelerated ions By supplying accelerated ions, a dense titanium nitride film can be formed on each of the surfaces 12a to 12e of the sample 12.
  • the film forming conditions at this time are as follows: the heating temperature of the sample 12 is 300 ° C., and the introduction ratio of argon gas and nitrogen gas is argon gas 130 SCCM (Standard Cubic Centimeter per Minute: 0 ° C., flow rate cc / min at 1 atm. Nitrogen gas is 40 SCCM, the degree of vacuum is 1.23 ⁇ 10 ⁇ 2 Pa, and the deposition rate is 5 ⁇ / sec. A 10 kW plasma gun manufactured by JEOL Ltd. was used as the plasma gun.
  • the film thickness, spectral transmittance, and spectral reflectance of the single layer titanium nitride film obtained by the above test film formation are measured, and known data, for example, the surface reflectance and film thickness of the sample 12 before film formation are measured.
  • the spectral reflection characteristics of the titanium nitride film were analyzed for each wavelength, and the values of the refractive index n and the extinction coefficient k were obtained by calculation.
  • the calculated values of the refractive index n and the extinction coefficient k are as shown in FIG. 8, and it was confirmed that each has wavelength dependency.
  • the solid line is the result when the substrate temperature of sample 12 is set to 300 ° C.
  • the refractive index n of the titanium nitride film is in the range of “2.0 ⁇ n ⁇ 3.0” in the wavelength range of 350 nm to 800 nm, as can be seen from the measurement result of FIG.
  • the extinction coefficient k needs to be in the range of “0.5 ⁇ k ⁇ 1.5”.
  • the titanium nitride film is used as a thin film having a higher refractive index than the silicon nitride film.
  • the refractive index n is high.
  • the refractive index n is below the lower limit, it becomes difficult to obtain spectral reflectance characteristics with wavelength selectivity, and the number of thin films increases in order to obtain desired characteristics. This has the disadvantage of increasing manufacturing costs.
  • the extinction coefficient k has a value of about “2.0” at most in the visible light range, but the metal film has an extinction coefficient as seen in the aluminum thin films listed in Table 1. k reaches “5.61922” at the center wavelength ⁇ 0 .
  • n 0.83413
  • the characteristics are as shown in FIG. According to this spectral reflection characteristic, even though a metal film is used, the total amount of reflected light is about 35% at the short wavelength side, and a light cyan color is observed sunk darkly, and a unique hue can be obtained. Recognize. Also in the embodiment using such a metal film, the refractive index n of one thin film is in the range of “1.36 to 3.5”, and the extinction coefficient k is in the range of “0.1 to 6”. That is satisfied.
  • FIG. 10 schematically shows the process.
  • a peelable adhesive layer 21 is applied to a base film 20 that serves as a support for the optical interference thin film, and a hard coat layer 22 for protecting the optical interference thin film is formed thereunder.
  • a film For the base film 20, a sheet made of PET (polyethylene terephthalate) can be suitably used.
  • an optical interference thin film 24 is formed under the hard coat layer 22.
  • the laminated body obtained in the steps up to FIG. 10B is cut according to the housing size of the product, and the insert part 25 is obtained.
  • the front and back of the optical interference thin film 24 of the insert part 25 are reversed and inserted into the lower mold 26, and then the upper mold 27 is aligned.
  • the casing 28 is molded by injection into a cavity between the molds.
  • the insert part 25 is integrally formed with the housing 28.
  • the base film 20 is peeled off together with the adhesive layer 21 from the molded product taken out from the mold.
  • an optical interference thin film 24 covered with the protective hard coat layer 22 is finally formed on the surface of the housing 28.
  • the present invention has been described based on the illustrated embodiment.
  • the film configuration of the interference thin film layer Ls it is possible to obtain spectral reflection characteristics that darkly reflect various color lights.
  • the spectral reflection characteristics similar to those in FIG. 2 can be obtained even by film formation by the reactive sputtering method, and various methods other than ion plating can be used as the film formation method. it can.
  • plating can be used for forming a metal film, and an approximately equivalent refractive index n and extinction coefficient k can be obtained.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Selon la présente invention, une couche métallique (L1) est formée sur un substrat sous-jacent (3), et une couche de revêtement interférentiel (Ls) stratifiant des couches de revêtement (L2 à L8) ayant des indices de réfraction différents (n) est disposée sur ladite couche métallique. Une couche protectrice transparente (L9) est formée sur la surface de la couche de revêtement interférentiel (Ls). La couche de revêtement interférentiel (Ls) module l'intensité de la lumière réfléchie en fonction de la longueur d'onde et la quantité de lumière réfléchie est maintenue à un niveau bas par l'absorption de lumière des couches de revêtement (L2, L4, L8), produisant ainsi une couleur extérieure ayant une teinte de couleur unique. Lorsque l'indice de réfraction complexe (N) des couches de revêtement (L2, L4, L8) est représenté par « N = n – ik » à l'aide de l'indice de réfraction (n), d'un coefficient d'extinction (k) et d'un nombre imaginaire (i), les relations suivantes sont satisfaites : « 1,36 ≤ n ≤ 3,5 » et « 0,1 ≤ k ≤ 6 ».
PCT/JP2009/066249 2008-09-18 2009-09-17 Revêtement interférentiel optique WO2010032783A1 (fr)

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Application Number Priority Date Filing Date Title
JP2008239722A JP2010072347A (ja) 2008-09-18 2008-09-18 光学干渉薄膜
JP2008-239722 2008-09-18

Related Child Applications (1)

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US13/419,947 Continuation US8330196B2 (en) 2009-09-18 2012-03-14 Semiconductor device and method of manufacturing the same

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WO2010032783A1 true WO2010032783A1 (fr) 2010-03-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11752729B2 (en) 2018-07-17 2023-09-12 3M Innovative Properties Company Conformable color shifting laminates

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7099743B2 (ja) 2019-12-03 2022-07-12 尾池工業株式会社 装飾フィルム

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11258405A (ja) * 1998-03-12 1999-09-24 Toppan Printing Co Ltd 反射防止フィルム
JP2000029006A (ja) * 1998-07-13 2000-01-28 Sharp Corp 低反射薄膜基板、カラーフィルタ基板および液晶ディスプレイ
JP2001159712A (ja) * 1999-09-20 2001-06-12 Sony Corp 光学フィルター、表示装置及び表示装置用前面板
JP2003029169A (ja) * 2001-07-12 2003-01-29 Sony Corp 光学多層構造体およびその製造方法、並びに光スイッチング素子および画像表示装置
WO2004031813A1 (fr) * 2002-10-02 2004-04-15 Bridgestone Corporation Film antireflet
JP2007140146A (ja) * 2005-11-18 2007-06-07 Nikon Corp 多層膜反射鏡及び露光装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11258405A (ja) * 1998-03-12 1999-09-24 Toppan Printing Co Ltd 反射防止フィルム
JP2000029006A (ja) * 1998-07-13 2000-01-28 Sharp Corp 低反射薄膜基板、カラーフィルタ基板および液晶ディスプレイ
JP2001159712A (ja) * 1999-09-20 2001-06-12 Sony Corp 光学フィルター、表示装置及び表示装置用前面板
JP2003029169A (ja) * 2001-07-12 2003-01-29 Sony Corp 光学多層構造体およびその製造方法、並びに光スイッチング素子および画像表示装置
WO2004031813A1 (fr) * 2002-10-02 2004-04-15 Bridgestone Corporation Film antireflet
JP2007140146A (ja) * 2005-11-18 2007-06-07 Nikon Corp 多層膜反射鏡及び露光装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11752729B2 (en) 2018-07-17 2023-09-12 3M Innovative Properties Company Conformable color shifting laminates

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