TWI417565B - Layer system for wipe-resistant reflectors and process for their production - Google Patents

Layer system for wipe-resistant reflectors and process for their production Download PDF

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TWI417565B
TWI417565B TW097107266A TW97107266A TWI417565B TW I417565 B TWI417565 B TW I417565B TW 097107266 A TW097107266 A TW 097107266A TW 97107266 A TW97107266 A TW 97107266A TW I417565 B TWI417565 B TW I417565B
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layer
metal
thickness
reflection
degree
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TW200900726A (en
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Torsten Schmauder
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Leybold Optics Gmbh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00596—Mirrors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00865—Applying coatings; tinting; colouring
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Ophthalmology & Optometry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Optical Elements Other Than Lenses (AREA)

Description

在一基質上之耐擦拭的反射器用的層系統和其製造方法 Layer system for a wiper resistant reflector on a substrate and method of making same

本發明關於一種在一基質上的耐擦拭的反射器用的層系統，包含一個光學反射金屬層和一個在該基質上設在金屬層相反側的透明層構造，該層構造具有一蓋層，由一電漿輔助析出的硬層構成，該硬層係以至少一種矽有機化合物為基礎者，且該層構造還可具有至少一中間層，其中，該上層構造的層厚度選設成使得和該上層構造的層厚度有關的光譜平均反射程度有一最大值Rmax ，且和該上層構造的層厚度有關的反射程度的光譜平均值RS 的值>Rmetal －1/3△R，其中Rmetal 係為該未保護的金屬層之一個類似於RS 測定的反射程度的一個類似於RS 所形成的光譜平均值，而△R＝Rmetal －Rmin ，且Rmin 表示該依上層構造的層厚度而定的反射程度的最小值，或者在該與上層構造的層厚度有關的顏色印象FS ＝(L＊ s ，a＊ s ，b＊ s )與該未受保護的金屬層的顏色印象Fm ＝(L＊ m ,a＊ m ,b＊ m )之間有一段顏色間隔 。此外還關於一種製造這種層系統的方法。The present invention relates to a layer system for a wipe resistant reflector on a substrate comprising an optically reflective metal layer and a transparent layer construction on the substrate opposite the metal layer, the layer construction having a cap layer a plasma-assisted precipitation hard layer composition, the hard layer being based on at least one cerium organic compound, and the layer structure may further have at least one intermediate layer, wherein the layer thickness of the upper layer structure is selected such that The spectral average reflection degree of the layer thickness of the upper layer structure has a maximum value R max , and the value of the spectral average value R S of the degree of reflection relating to the layer thickness of the upper layer structure is > R metal - 1/3 ΔR, where R metal a system for the unprotected metal layer similar to the degree of reflection R S is a measured spectrum similar to the average of the formed R S, and △ R = R metal -R min, and R min represents the configuration of the upper layer by a minimum value of the degree of reflection depending on the layer thickness, or a color impression F S = (L * s , a * s , b * s ) associated with the layer thickness of the upper layer structure and the color of the unprotected metal layer Impression F m = (L There is a color interval between * m , a * m , b * m ) . There is also a method of manufacturing such a layer system.

許多燈具除了本身的光源(燈泡、燈管)外，還使用一個或數個反射性表面(反射器)以改變光路徑以及改變照明作用以及分佈。今日許多這類反射器由一塑膠模製件構成，其表面鍍金屬而得到反射器功能。在一些應用領域，上述反射器在製造時(例如在個別部件運送及燈具安裝 時)或在燈具的整個使用壽命過程中(例如作洗洗)時受到機械應力。Many luminaires use one or more reflective surfaces (reflectors) in addition to their own light sources (bulbs, tubes) to change the light path and to change the illumination and distribution. Many of these reflectors today consist of a plastic molded part that is metallized to provide a reflector function. In some applications, the above reflectors are manufactured (eg in individual component transport and luminaire installation) Mechanical stress is applied during the entire life of the luminaire (for example, for washing).

在性質上，對於反射器一般希望至少在一波長範圍中(在此範圍中該燈具要當作光源)的光要有儘量最高的反射，典型的範圍係對人眼可見的頻域，約400奈米~約800奈米。In nature, it is generally desirable for the reflector to have at least one wavelength range (in which the luminaire is to be used as a light source) with the highest possible reflection, typically in the frequency domain visible to the human eye, about 400. Nano ~ about 800 nm.

塑膠表面以及一般利用真空鍍金屬製造的鍍覆層極易受機械性刮傷。為了避免該構件早夭(往往在燈具安裝時已會發生)，故需要一附加之機械性保護覆層。迄今，此覆層一般係利用上漆製造。Plastic surfaces and coatings typically made by vacuum metallization are highly susceptible to mechanical scratching. In order to avoid early failure of the component (which often occurs when the luminaire is installed), an additional mechanical protective coating is required. To date, this coating has generally been manufactured using lacquering.

具有一透明硬蓋層的室內下照燈反射器(Indoor－Downlight－Reflektor)的覆層係習知者。例如在德專利DE 196 34 334 C1中所述，有各種不同的相關方法以製造具有一光學反射器層及一封閉之護層的反射覆層。依一第一方法係作真空鍍金屬，藉此構成一由金屬構成的反射層，再利用浸覆或射出方法將一封閉的護漆施在該反射層上，該護漆保護反射層以免受機械應力(例如擦拭)損壞。在此方法中，由於真空鍍覆及上漆的方法步驟互相分離，它們需一真空鍍覆室及一浸覆或射出設備，因此投資成本提高，由於在上漆程序，因為形成灰塵及液滴造成品質的損失(Einbu)導致廢品率提高，因此成本更進一步提高。此外，上漆不牢的情形也屢見不鮮。A coating of an Indoor-Downlight-Reflektor with a transparent hard cover is known. A variety of different methods are known for producing a reflective coating having an optical reflector layer and a closed sheath, as described in German Patent No. DE 196 34 334 C1. According to a first method, vacuum metallization is used to form a reflective layer made of metal, and a closed paint is applied to the reflective layer by a dip or injection method, and the paint protects the reflective layer from Mechanical stress (such as wiping) is damaged. In this method, since the vacuum plating and painting method steps are separated from each other, they require a vacuum plating chamber and a dipping or injection device, so the investment cost is increased due to the painting process because dust and droplets are formed. Causing loss of quality (Einbu ) The scrap rate is increased, so the cost is further increased. In addition, the situation of not being lacquered is not uncommon.

在第二種方法，反射鍍覆層設以一種電漿輔助析出的護層。在此，在一個利用真空鍍金屬造成的反射性金屬層 上，利用電漿聚合方法製造一硬的蓋層。In the second method, the reflective plating layer is provided with a plasma-assisted protective layer. Here, in a reflective metal layer caused by vacuum metallization In the above, a hard cap layer is produced by a plasma polymerization method.

舉例而言，一機械性護層可藉著將矽有機化合物與氧利用電漿轉變(PECVD)而製造。所用之矽有機物的例子為六甲基二矽氧烷(HMOSO)或四甲基二矽氧烷(TMDSO)。所用之氧的來源除了氧(O2 )外還有臭氧(O3 )、一氧化二氮(N2 O)或其他能提供氧的物質。利用PECVD從矽氧烷製造硬層的說明，舉例而言見於文獻DE 3413 019 A1及EP 007 48259 B1。For example, a mechanical sheath can be made by plasma-transformed (PECVD) organic compounds with oxygen. An example of the ruthenium organic material used is hexamethyldioxane (HMOSO) or tetramethyldioxane (TMDSO). The source of oxygen used is ozone (O 3 ), nitrous oxide (N 2 O) or other oxygen-providing substances in addition to oxygen (O 2 ). A description of the production of hard layers from decane by PECVD is known, for example, from the documents DE 34 13 019 A1 and EP 007 48259 B1.

製造以矽氧烷為基礎的硬層當作護層以防機械性負荷(特別是擦傷)的做法，要和利用PECVD從矽有化合物不加氧製造化學護層(特別是耐腐蝕護層)的做法有區別別。舉例而言，這類防腐護層係用於保護車燈的反射器上的反射性鋁層者，例如DE 2537 416 A1所述者。The manufacture of a hard layer based on decane as a sheath to prevent mechanical loads (especially scratches), and the use of PECVD to produce chemical barriers (especially corrosion resistant coatings) from bismuth compounds without oxygen There is a difference in the practice. For example, such an anti-corrosion coating is used to protect a reflective aluminum layer on a reflector of a vehicle lamp, such as that described in DE 2537 416 A1.

利用矽氧烷不加氧用PECVD所得之層的性質係和一種矽力康橡膠相似。它們係柔軟、有彈性、具高度化學抵抗性。在本發明的範疇中，這類層在以下稱為矽氧烷防腐蝕護層。The properties of the layer obtained by PECVD using non-oxygenated azepine are similar to those of a lyricone rubber. They are soft, elastic and highly chemically resistant. Within the scope of the present invention, such layers are referred to below as decane anticorrosive coatings.

而利用PECVD從矽氧烷加氧所得的層則和玻璃更相似。它們係透明、硬且脆。以下這些層稱為矽氧烷硬層。The layer obtained by oxygenation from alumoxane by PECVD is more similar to glass. They are transparent, hard and brittle. The following layers are referred to as a hard layer of decane.

此外，習知技術還有利用梯度層，以分段或無段式方式從彈性之底層過渡變到耐刮損的蓋層，而使該硬層有利地配合該同樣地較軟的塑膠基質。其例子為上述之DE 34130 19 A1。In addition, the prior art also utilizes a gradient layer that transitions from a resilient underlayer to a scratch-resistant cap layer in a segmented or non-segmented manner, such that the hard layer advantageously fits into the same softer plastic matrix. An example of this is DE 34 130 19 A1 above.

將塑膠基質上之受保護以防機械性損壞的金屬反射層 的層系統的計的一重要特點為層的順序。一種良好的保護係藉著將該硬層施到金屬層上之背向基質的那一側上而達成。但在此有一缺點：該護層須被要反射的光通過，因此它會造成反射程度的損失，大致係由於在硬層中吸收以及干涉造成，此外這些損失和波長有關，且造成不想要的顏色效果。a metal reflective layer on a plastic substrate that is protected from mechanical damage An important feature of the layer system is the order of the layers. A good protection is achieved by applying the hard layer to the side of the metal layer that faces away from the substrate. However, there is a disadvantage in that the sheath must pass through the light to be reflected, so that it causes a loss of reflection, which is mainly due to absorption and interference in the hard layer, and these losses are related to the wavelength and cause unwanted Color effect.

為了硬保一種電漿CVD(PCVD)層在實用上有充分之防刮損的作用，故需要有某種層厚度，其中在較厚的層的場合，會發生反射光顏色混淆。在DE 1 96 34 334 C1中，為了提高薄的HMDSO層的機械穩性，係主張將該防止刮損的保護作用的層的儘量多的部分放到反射式金屬層下方，而只有一小部分呈硬蓋層的形式施到反射性金屬層上。因此依DE 196 34 334 C1，一個厚度50~100奈米的HMCSO蓋層被金屬層下方的一厚硬的底層支持，且在製造時，該HMDSO蓋層被金屬層下方的一厚硬的底層支持，且在製造時，該HMDSO蓋層的析出作用在一厚度時(在此厚度時就開始形成干涉色)就終止。In order to ensure that a plasma CVD (PCVD) layer is practically sufficiently scratch-resistant, a certain layer thickness is required, and in the case of a thick layer, color confusing of reflected light occurs. In DE 1 96 34 334 C1, in order to increase the mechanical stability of the thin HMDSO layer, it is claimed that as much of the layer of the protective layer that prevents scratching is placed under the reflective metal layer, with only a small portion It is applied to the reflective metal layer in the form of a hard cover layer. Thus, according to DE 196 34 334 C1, a HMCSO cap layer having a thickness of 50 to 100 nm is supported by a thick hard underlayer beneath the metal layer, and at the time of manufacture, the HMDSO cap layer is formed by a thick underlayer under the metal layer. Supported, and at the time of manufacture, the precipitation of the HMDSO cap layer terminates at a thickness at which the interference color begins to form.

本發明的目的在提供一種耐擦拭的光反射器用的層系統以及一種製造這種層系統的方法，該系統有一個具充分耐刮損性的硬蓋層，同時其光學印象相對於所要保護的金屬層來，儘量不會混淆。It is an object of the present invention to provide a layer system for a wipe resistant light reflector and a method of manufacturing such a layer system having a hard cover layer having sufficient scratch resistance while having an optical impression relative to the desired protection Metal layers come as far as possible without confusion.

此目的係利用申請專利範圍獨立項的特點達成。This purpose is achieved by using the characteristics of the independent scope of the patent application.

依本發明這種目的解決之道係由一種在一基質上的耐 擦拭的反射器用的層系統著手，該系統包含一個光學反射金屬層和一個在該基質上設在金屬層相反側的透明層構造，該層構造具有一蓋層，由一電漿輔助析出的硬層構成，該硬層係以至少一種矽有機化合物為基礎者，且該層構造還可具有至少一中間層，其中，該上層構造的層厚度選設成使得和該上層構造的層厚度有關的光譜平均反射程度有一最大值Rmax 。This object is solved by a layer system for a wipe resistant reflector on a substrate comprising an optically reflective metal layer and a transparent layer disposed on the opposite side of the metal layer on the substrate. Constructed, the layer structure has a cap layer composed of a plasma-assisted hard layer, the hard layer is based on at least one cerium organic compound, and the layer structure may further have at least one intermediate layer, wherein The layer thickness of the superstructure is chosen such that the spectral mean reflection level associated with the layer thickness of the superstructure has a maximum value Rmax .

本發明係根據一項認知：隨著上層構造(特別是蓋層)的層厚度增加，不想要的效果－－例如由於和波長有關的干涉造成之漸增的顏色混淆作用隨著化的反射程度在各光譜範圍發生且使反射程度減少，然而在蓋層的一定厚度的範圍中，這種效果減少，且反射的顏色印象相對於未受保護的金屬層來，顯得更中性。當上層構造的層厚度進一步提高超出該區域時，則反射程度遽降(特別是在短波長的場合)，且因此反射光的顏色混淆情事加大。當層厚度更進一步增加時，得到具有大致中性顏色印象的重新反射的光。出乎意料地，可用以下方法達成極小的顏色混淆，將上層構造的層厚度顯設成使平均之光譜反射程度有一最大值Rmax 。The invention is based on the recognition that as the layer thickness of the superstructure (especially the cap layer) increases, unwanted effects - for example, due to wavelength-dependent interference, the increasing color confusing effect This occurs in the spectral range and reduces the degree of reflection, however in the range of a certain thickness of the cap layer, this effect is reduced and the reflected color impression is more neutral with respect to the unprotected metal layer. When the layer thickness of the upper layer structure is further increased beyond the area, the degree of reflection is reduced (especially in the case of short wavelengths), and thus the color confounding of the reflected light is increased. As the layer thickness is further increased, re-reflected light having a substantially neutral color impression is obtained. Unexpectedly, minimal color confusing can be achieved by the following method, the layer thickness of the upper layer construction being set such that the average spectral reflectance has a maximum value Rmax .

上述對於所產生之反射器之儘量最大的反射的要求往往伴隨另一種要求－－不能由於光譜中不同頻率吸收不同或干涉造成不要的頻色印象。這種組合的要求需要品質標準配合各用途，以評估所予之層系統的性質，其中依本發明，係用反射程度之光譜平均值RS 當作標準。The above requirements for the greatest possible reflection of the resulting reflector are often accompanied by another requirement that no unwanted color impressions can be caused by different absorption or interference at different frequencies in the spectrum. This request requires a combination with the quality standards for each application to evaluate the properties of the layer to the system, which under this invention, the spectral line with the average of the degree of reflection R S as a standard.

所用之反射程度的光譜平均值RS 的定義係為所測的反射程度的平均值，係在反射的光線的一預設波長範圍中用一適當之權重函數形成，此波長範圍對於在可見光譜中的應用係在360奈米~830奈米範圍，但最少包含400奈米~700奈米範圍。平均值係利用一種與具體使用情形有關的權重函數形成。舉例而言，在最簡單的情形可使用一術平均值，雖然其他函數也很有用。The spectral mean value R S of the degree of reflection used is defined as the average of the degree of reflection measured, which is formed by a suitable weighting function over a predetermined wavelength range of the reflected light for the visible spectrum. Applications range from 360 nm to 830 nm, but at least 400 nm to 700 nm. The average is formed using a weight function associated with the particular use case. For example, in the simplest case an average can be used, although other functions are also useful.

反射程度的光譜平均值之計算的具體方法係配合反射器的各具體目的針對波長範圍以及其中所含波長的相對權重(反射器要在該範圍中工作)。一習知之方法係測定顏色座標L＊ 、a＊ 與b＊ 。The specific method of calculating the spectral mean of the degree of reflection is in accordance with the specific purpose of the reflector for the wavelength range and the relative weight of the wavelengths contained therein (the reflector is to operate in this range). A conventional method is to measure the color coordinates L * , a * and b * .

用於心理顏色刺激辨識的標準系統(由CIE委員會開發)稱為L＊ a＊ b＊ 。顏色系統(Commission international e del’clairage，刊物CIE No.15.2,Colorimetry，第二版，Central Bureau of the CIE,Vienna,1986)，例如在ASTM Designation 308－01所述(Standard Practice for Computing the Colors of Objects by Using the CIE System,2001年11月)。A standard system for the identification of mental color stimuli (developed by the CIE committee) is called L * a * b * . Color system (Commission international e del' Clairage, Publication CIE No. 15.2, Colorimetry, Second Edition, Central Bureau of the CIE, Vienna, 1986), for example, in ASTM Designation 308-01 (Standard Practice for Computing the Colors of Objects by Using the CIE System, 2001). November of the year).

在本發明，該顏色印象L＊ a＊ b＊ 係用一CIE標準照明的(宜為D65)觀測器(且宜2∘或10∘)求出。舉例而言，要測量光譜反射程度，可使用X－Rite公司(4300 44th Street SE Grand Rapids,MI,49512 USA)的顏色測量儀器Model SP60。In the present invention, the color impression L * a * b * is determined using a CIE standard illuminated (preferably D65) observer (and preferably 2 or 10 inches). For example, to measure the degree of spectral reflectance, a color measuring instrument Model SP60 from X-Rite Corporation (4300 44 th Street SE Grand Rapids, MI, 49512 USA) can be used.

由於反射程度和反射之光線的觀看角度以及入射角度有關，因此反射程度沿在反射器一典型觀看位置的方向且 對入射光的一典型入射角度測度。Since the degree of reflection is related to the viewing angle of the reflected light and the angle of incidence, the degree of reflection is in the direction of a typical viewing position of the reflector and A typical incident angle measure of incident light.

依本發明另一特點，上層構造的層厚度選設成使得和該上層構造的層厚度有關的光譜平均反射程度有一最大值Rmax 。According to another feature of the invention, the layer thickness of the superstructure is chosen such that the spectral average reflection level associated with the layer thickness of the superstructure has a maximum value Rmax .

和該上層構造的層厚度有關的反射程度的光譜平均值RS 的值>Rmetal －1/3△R，其中Rmetal 係為該未保護的金屬層之一個類似於RS 測定的反射程度的一個類似於RS 所形成的光譜平均值，而△R＝Rmetal －Rmin ，且Rmin 表示該依上層構造的層厚度而定的反射程度的最小值，或者在該與上層構造的層厚度有關的顏色印象FS ＝(L＊ s ,a＊ s ,b＊ s )與該未受保護的金屬層的顏色印象Fm ＝(L＊ m ,a＊ m ,b＊ m )之間有一段顏色間隔 。The spectral mean value R S of the degree of reflection associated with the layer thickness of the superstructure is > R metal - 1/3 ΔR, where R metal is a degree of reflection of the unprotected metal layer similar to the R S measurement One is similar to the average value of the spectrum formed by R S , and ΔR = R metal - R min , and R min represents the minimum value of the degree of reflection depending on the layer thickness of the upper layer structure, or in the structure with the upper layer The color impression of the layer thickness F S = (L * s , a * s , b * s ) and the color impression of the unprotected metal layer F m = (L * m , a * m , b * m ) There is a color interval between .

此類似RS 形成之光譜平均值Rmetal 係用和RS 相同的權重函數以及經由和RS 相同的波長範圍形成。該未受保護的金屬層之和RS 相似地測定的反射程度係在和該與上層構造層厚度有關的反射程度相同的條件下及相同的測量方法測定。Similarly the average spectral lines R S R metal forming purposes and the same weights and weight function R S and R S formed via the same wavelength range. The degree of reflection of the unprotected metal layer similarly measured by R S is measured under the same conditions as the degree of reflection associated with the thickness of the upper structural layer and the same measurement method.

用於心理顏色刺激辨識的標準系統(由CIE委員會開發)稱為L＊ a＊ b＊ 。顏色系統(Commission international e delclairage，刊物CIE No.15.2,Colorimetry，第二版，Central Bureau of the CIE,Vienna,1986)，例如在ASTM Designation 308－01所述(Standard Practice for Computing the Colors of Objects by Using the CIE System,2001年11月)。A standard system for the identification of mental color stimuli (developed by the CIE committee) is called L * a * b * . Color system (Commission international e del Clairage, Publication CIE No. 15.2, Colorimetry, Second Edition, Central Bureau of the CIE, Vienna, 1986), for example, in ASTM Designation 308-01 (Standard Practice for Computing the Colors of Objects by Using the CIE System, 2001). November of the year).

在本發明，該顏色印象L＊ a＊ b＊ 係用一CIE標準照明的(宜為D65)觀測器(且宜2∘或10∘)求出。舉例而言，要測量光譜反射程度，可使用X－Rite公司(4300 44th Street SE Grand Rapids,MI,49512 USA)的顏色測量儀器Model SP60。In the present invention, the color impression L * a * b * is determined using a CIE standard illuminated (preferably D65) observer (and preferably 2 or 10 inches). For example, to measure the degree of spectral reflectance, a color measuring instrument Model SP60 from X-Rite Corporation (4300 44 th Street SE Grand Rapids, MI, 49512 USA) can be used.

如果依本發明，上層構造的層厚度選設成使得一反射程度(它與上反射構造的層厚度有關)的光譜平均值RS 的值>Rmetal －1/3△R，則得到一種光學反射，其反射光大致不會混淆，且它同時具有高度耐擦拭及刮損強度。在此，Rmetal 係為該未保護的金屬層之一類似RS 測定的反射程度的一種類似於RS 形成的光譜的平均值，而△R＝Rmetal －Rmin ，其中Rmin 表示該與上層構造的層厚度有關的反射程度RS－ 的最小值。在一較佳實施例中，對選設之上層構造的層厚度，一種與上層構造的層厚度有關的反射程度的光譜平均值RS 為>Rmetal －c△R，其中c在1/10到1/4範圍。According to the invention, the layer thickness of the superstructure is chosen such that the value of the spectral mean value R S of a degree of reflection (which is related to the layer thickness of the upper reflection structure) > R metal - 1/3 ΔR gives an optical Reflection, the reflected light is not substantially confused, and it is also highly resistant to wiping and scratching. Here, one of R metal lines for the unprotected metal layer similar to the degree of reflection of a structured R S mean value measured spectrum similar structured R S is formed, and △ R = R metal -R min, wherein R min represents the The minimum value of the degree of reflection R S- associated with the layer thickness of the superstructure. In a preferred embodiment, the spectral average value R S of the layer thickness of the selected upper layer structure, the degree of reflection associated with the layer thickness of the upper layer structure is >R metal -cΔR, where c is 1/10 To the 1/4 range.

出乎意料地，全球性參數Rmetal 和△R適用於將上層系統的層厚度測定，使得該層系統的顏色印象大致為中性者。Unexpectedly, the global parameters R metal and ΔR are suitable for determining the layer thickness of the upper system such that the color impression of the layer system is substantially neutral.

如不採此方式，則建議使用該L＊ a＊ b＊ 顏色系統以代表反射光特性，且將上層構造的層厚度選設成使得在一個與上層構造層厚度有關的顏色印象FS ＝(L＊ s ,a＊ s ,b＊ s )與一未保護之金屬層的顏色印象Fm ＝(L＊ m ,a＊ m ,b＊ m )之間有一段顏色距離△E＊ ，△E＊ <2.0。If this is not the case, it is recommended to use the L * a * b * color system to represent the reflected light characteristics, and to select the layer thickness of the upper layer structure such that a color impression associated with the thickness of the upper layer is F S =( L * s , a * s , b * s ) has a color distance ΔE * , ΔE between the color impression F m = (L * m , a * m , b * m ) of an unprotected metal layer * <2.0.

依本發明此特點，顏色印象係依上層構造的層厚度而 定與未受保護的金屬層的顏色印象比較。此L＊ a＊ b＊ 顏色系統係基於人感覺的性質，且比(例如)反射程度的算術平均值更適合用於代表光學反射器的顏色印象的特性。L＊ 為亮度的一種值，a＊ 為顏色印象紅－綠值，b＊ 為顏色印象的黃－藍值。According to this feature of the invention, the color impression is compared to the color impression of the unprotected metal layer depending on the layer thickness of the upper layer structure. This L * a * b * color system is based on human sensation properties and is more suitable for representing the color impression of the optical reflector than, for example, the arithmetic mean of the degree of reflection. L * is a value of brightness, a * is the color impression red-green value, and b * is the yellow-blue value of the color impression.

上層構造的層厚度在110奈米~200奈米的範圍。厚度宜為由130奈米到150奈米(特別是對於以矽氧烷為基礎的硬層)。The layer thickness of the upper structure is in the range of 110 nm to 200 nm. The thickness is preferably from 130 nm to 150 nm (especially for a hard layer based on decane).

蓋層的層厚度宜在110奈米~190奈米之間的範圍，如此可達到層系統的高耐擦傷強度。The layer thickness of the cap layer is preferably in the range of between 110 nm and 190 nm, so that the high scratch resistance of the layer system can be achieved.

本發明可用於不同反射器：一汽車之車頭燈反射器(它係初級反射器)設計成使所用之照明手段的特定光束有最佳反射者，其中該平均值的形成在大多為較短波(藍光)鹵素燈或氙氣燈輻射線的份量比較長波的輻射線強。The invention can be used with different reflectors: a headlight reflector of an automobile (which is a primary reflector) is designed to have an optimum reflection of a particular beam of illumination used, wherein the average is formed in mostly shorter waves ( Blu-ray) The amount of radiation from a halogen or xenon lamp is stronger than that of a long wave.

在先前技術框部分〔圖框(Bezel)〕舉例而言，迄今往往用電鍍方式鍍鉻，鍍覆上一硬覆層。由於電鍍覆層(特別是鉻電鍍)需要較大量的有毒物質，故使用這種方法要花較大成本在程序安全及廢棄處理上，因此基本上要避免。For example, in the prior art frame (Bezel), chrome plating has been used so far, and a hard coating is applied. Since electroplating coatings (especially chrome plating) require a relatively large amount of toxic substances, the use of this method is costly in terms of program safety and disposal, and thus is basically avoided.

一框要將金屬層之一定之裝飾性顏色再生，因此依本發明達到顏色距離△E＊ <2。A frame is required to reproduce a certain decorative color of the metal layer, so that the color distance ΔE * <2 is achieved according to the invention.

要將舒適作用的白光分佈的天花板燈，對於具有光譜平均值的儘量最好的反射而言，係對應於人眼的敏感度作 最佳化。The ceiling light to distribute the comfortable white light, for the best possible reflection with the spectral mean, corresponds to the sensitivity of the human eye. optimization.

依本發明，可使用比迄今更厚之上護層，因為利用本發明的層系統可避免一般的顏色混淆(摻雜)及反射損失(Einbu)。由於層系統的耐擦傷強度隨蓋層厚度增加，故依本發明可提供具高度耐擦拭及刮損的強度的光學反射器，同時有高光學品質。According to the invention, it is possible to use a thicker overcoat than heretofore, since the general color confounding (doping) and reflection loss can be avoided by using the layer system of the invention (Einbu ). Since the scratch resistance of the layer system increases with the thickness of the cover layer, according to the present invention, an optical reflector having a high resistance to wiping and scratching can be provided while having high optical quality.

在本發明一有利的進一步特點中，在金屬層之朝向基質的那一側上設有一底層，它提高金屬層在基質上的附著性或層系統的機械穩定性。In an advantageous further feature of the invention, a primer layer is provided on the side of the metal layer facing the substrate which increases the adhesion of the metal layer to the substrate or the mechanical stability of the layer system.

底層可為一受電漿輔助析出的層。該層係以至少一種矽有機化合物為基礎，最好使用一硬底材料，它可防止設在其上方的層的機械性斷裂，而且如果要避免蓋層厚度增加(因為否則的話，反射器的光學印象會變差)也能夠進一步提高耐括損強度。The bottom layer can be a layer that is supported by the plasma. The layer is based on at least one bismuth organic compound, preferably a hard bottom material which prevents mechanical breakage of the layer disposed above it, and if the thickness of the cover layer is to be avoided (because otherwise, the reflector The optical impression is also deteriorated) and the damage resistance can be further improved.

在本發明另一特點中，在蓋層與金屬層之間至少設有一中間層。此上中間層宜具有保護金屬層以防氧化的功能。In another feature of the invention, at least one intermediate layer is disposed between the cover layer and the metal layer. The upper intermediate layer preferably has a function of protecting the metal layer from oxidation.

此外，在底層與金屬層之間可設至少一附加的中間層，特別是具有保護金屬層以防氧化的功能。Furthermore, at least one additional intermediate layer can be provided between the underlayer and the metal layer, in particular with a protective metal layer for oxidation protection.

下中間層及/或上中間層的層厚度宜在10奈米與20奈米之間。此處宜使用上文稱文矽氧烷腐蝕防護層的習知護層。The layer thickness of the lower intermediate layer and/or the upper intermediate layer is preferably between 10 nm and 20 nm. It is preferred here to use a conventional sheath which is referred to above as a protective layer of the oxime oxide.

該矽有機化合物宜為HMDSO或TMDSO，它們利用一電漿裂解且呈層或層組成的形式析出，當製造該電漿輔助 析出的硬層時，氧及/或氮結合入一個層中，該層在製造時當作反應性成份供應。如習知者，此反應性成份以一和HMDSO或TMDSO對應成份1：0.5到1.20的流率比例供應。The cerium organic compound is preferably HMDSO or TMDSO, which is cleavage by a plasma and precipitated in the form of a layer or a layer, when the plasma is assisted When the hard layer is precipitated, oxygen and/or nitrogen are incorporated into a layer which is supplied as a reactive component at the time of manufacture. As is conventional, the reactive component is supplied at a flow rate ratio of 1:0.5 to 1.20 for HMDSO or TMDSO.

特別適用於光反射器的層係一種金屬層，它至少包含一種以下成份：鋁、銅、銀、金、鈦、鎂、鐵、鋼、鉻或這些東西形成的合金。金屬層的厚度宜在20~150奈米之間。本發明的層系統可以有效、廉價地用中頻到低頻的電磁波激發(例如以40仟赫的頻率)以高品質在一傳統的單室鍍覆設備中製造。A layer particularly suitable for use in a light reflector is a metal layer comprising at least one of the following components: aluminum, copper, silver, gold, titanium, magnesium, iron, steel, chromium or an alloy formed from these. The thickness of the metal layer should be between 20 and 150 nm. The layer system of the present invention can be efficiently and inexpensively fabricated with intermediate frequency to low frequency electromagnetic wave excitation (e.g., at a frequency of 40 kHz) in a conventional single chamber plating apparatus with high quality.

本發明其他特點與優點在以下配合圖式中的實施例說明，但其範圍不限於此。Other features and advantages of the present invention are described below in conjunction with the embodiments in the drawings, but the scope is not limited thereto.

圖1以示意方式顯示一本發明的層系統的構造，具有一基質(10)、一金屬層(20)、一蓋層(30)、一上中間層(40)、一底層(50)、及一下中間層(60)。基質宜為一塑膠基質(例如由聚羧酸酯構成者)或一光學反射器用的金屬層，金屬層(20)可為鋁、銅、銀、金、鈦、鎂、鐵、鋼、鉻或一由它們形成的合金，此合金利用濺鍍方法、物理或化學蒸鍍方法或離子束方法施覆者。蓋層(30)係一種受電漿輔助析出的硬層，它基於至少一種矽有機化合物為基礎且具有高度耐擦傷強度。底層(50)為一受電漿輔助析出的矽有機化合物或一漆層。它宜為硬層。上中間層(40)與下中間層(60)宜為電漿輔助析出的化合物，且以矽有機化合物為基礎 者，選用之矽有機化合物宜為HMDSO或TMDSO。Figure 1 shows in schematic form the construction of a layer system of the invention having a substrate (10), a metal layer (20), a cover layer (30), an upper intermediate layer (40), a bottom layer (50), And the middle layer (60). The substrate is preferably a plastic substrate (for example, composed of a polycarboxylate) or a metal layer for an optical reflector, and the metal layer (20) may be aluminum, copper, silver, gold, titanium, magnesium, iron, steel, chromium or An alloy formed by them which is applied by a sputtering method, a physical or chemical vapor deposition method or an ion beam method. The cap layer (30) is a plasma-assisted hard layer which is based on at least one cerium-based organic compound and has a high scratch resistance. The bottom layer (50) is a ruthenium organic compound or a lacquer layer which is supported by a plasma. It should be a hard layer. The upper intermediate layer (40) and the lower intermediate layer (60) are preferably plasma-assisted compounds and are based on cerium organic compounds. The organic compound selected should be HMDSO or TMDSO.

圖2中顯示一種層系統(它具有由一厚層及一選擇性之中間層的層構造)的平均反射層度R和層厚度的典型關係。典型的情形，反射程度隨著層厚度增加而從一種未保護的金屬層的值開始首先減少，並達到一最小值Rmin ，然後到一第一最大值，隨後再到另一最大值，而在最大值之間的最小值的值則增加，在本發明的層系統，該層構造的層厚度的值選設成使得平均反射程度R>Rmetal －1/3△R。 特佳的層系統的層厚度在第一或第二最大值的範圍中造成一種平均反射程度。在圖3的圖示中，層厚度在S1 或S2 的範圍。A typical relationship of the average reflective layer R and layer thickness of a layer system having a layer configuration of a thick layer and a selective intermediate layer is shown in FIG. Typically, the degree of reflection decreases first from the value of an unprotected metal layer as the layer thickness increases, and reaches a minimum value R min , then to a first maximum value, and then to another maximum value. The value of the minimum value between the maximum values is increased. In the layer system of the present invention, the value of the layer thickness of the layer construction is selected such that the average degree of reflection R > R metal - 1/3 ΔR. The layer thickness of a particularly good layer system results in an average degree of reflection in the range of the first or second maximum. In the illustration of Figure 3, the layer thickness is in the range of S 1 or S 2 .

要製造本發明的層系統，係將一光學反射器放入一鍍覆設備(例如本申請人的一種PolorMet 1V設備)的真空室中，在其中有雲母電極以供入電磁能量，並有磁子濺鍍陰極(它具有鋁製的靶)，反射器和靶對立設置，其中所要鍍覆之表面和靶對立。層之電漿輔助析出作用利用二個板電極達成，它們接在一40仟赫產生器，其最大功率為5仟瓦。To fabricate the layer system of the present invention, an optical reflector is placed in a vacuum chamber of a plating apparatus (e.g., a PolorMet 1V apparatus of the Applicant) in which a mica electrode is supplied with electromagnetic energy and magnetically The sub-sputter cathode (which has a target made of aluminum), the reflector and the target are disposed opposite each other, wherein the surface to be plated is opposed to the target. The plasma-assisted precipitation of the layers is achieved using two plate electrodes connected to a 40 Hz generator with a maximum power of 5 watts.

利用以下程序步驟將一種耐擦拭的層系統施到一個約3mm厚的聚羧酸酯基質上。A wipe resistant layer system was applied to a polycarboxylate matrix of about 3 mm thickness using the following procedure.

〔電漿預處理〕 真空室抽空到壓力3×10－2 毫巴。將氬氣體以約800 sccm導入真空室中，其中利用電磁能以5仟瓦功率及40仟赫頻率作約30秒激發一電漿。將基質利用該電漿清洗，並 活化以使以後的層有較佳之附著。[Pretreatment of plasma] The vacuum chamber was evacuated to a pressure of 3 × 10 -2 mbar. Argon gas was introduced into the vacuum chamber at about 800 sccm, wherein a plasma was excited by electromagnetic energy at a power of 5 watts and a frequency of 40 Hz for about 30 seconds. The substrate is washed with the plasma and activated to provide better adhesion to subsequent layers.

〔硬底層之電漿CVD〕 一個350奈米厚的層利用電層能在40仟赫之電磁激發的場合以4.5仟赫功率及150 sccm HMDSO及750 sccm氧的氣流在約4×10－2 毫巴的程序壓力在240秒的程序時期施加。[plasma CVD of hard underlayer] A 350 nm thick layer can be used in an electromagnetic layer of 40 kHz with a power of 4.5 Hz and a flow of 150 sccm HMDSO and 750 sccm of oxygen at about 4 × 10 -2 The program pressure of mbar is applied during the 240 second program period.

〔中間層的電漿CVD〕 在程序壓力4×10－2 毫巴將HMDSO以100 sccm的流率導入真空室中，且利用電磁能以4.5仟赫的功率及40仟赫的頻率作用約20秒觸發一電漿，其中一個約5~10奈米厚的中間層析出到基質上。[plasma CVD of the intermediate layer] HMDSO was introduced into the vacuum chamber at a flow rate of 10 × 10 -2 mbar at a flow rate of 100 sccm, and the electromagnetic energy was applied at a power of 4.5 kHz and a frequency of 40 kHz. A second is triggered by a plasma, and an intermediate of about 5-10 nm thick is chromatographed onto the substrate.

〔濺鍍一金屬層〕 將真空室抽空到基本壓力小於10－8 毫巴，然後在540 sccm的氬氣流在3×10－3 毫巴程序壓力及70仟瓦之濺鍍功率將一反射性鋁層(層厚度約80奈米)在約15秒的程序期間濺鍍。[sputtering a metal layer] evacuating the vacuum chamber to a base pressure of less than 10 -8 mbar, then argon at 540 sccm at a process pressure of 3 × 10 -3 mbar and a sputtering power of 70 watts will be reflective The aluminum layer (layer thickness about 80 nm) was sputtered during the procedure of about 15 seconds.

〔將一中間層作電漿CVD〕 在程序壓力4×10－2 毫巴將HMDSOO以100 sccm流率導入真空室，並利用電磁能以4.5仟瓦之功率及40仟赫頻率作用約20秒觸發一電漿，其中在基質上析出一層約5~10奈米厚的中間層。[Using an intermediate layer as a plasma CVD] The HMDSOO was introduced into the vacuum chamber at a flow rate of 10 × 10 -2 mbar at a flow rate of 100 sccm, and the electromagnetic energy was applied at a power of 4.5 watts and a frequency of 40 kHz for about 20 seconds. A plasma is triggered in which a layer of about 5-10 nm thick is deposited on the substrate.

〔蓋層之電漿CVD〕 將HMDSO以150 sccm流及將氧以600 sccm流率以400仟赫用4仟瓦電漿功率激發。在此步驟90秒的期間，將 一160奈米厚的護層析出，較短或較長的程序時間會造成較薄或較厚的護層。[plasma CVD of the cap layer] HMDSO was flowed at 150 sccm and oxygen was excited at 400 cc flow rate at 400 kHz with 4 watts of plasma power. During this step of 90 seconds, will A 160 nm thick protection chromatography results in a shorter or longer procedure time resulting in a thinner or thicker sheath.

在將該室通入空氣後，可將鍍覆過的基質拿出。After the chamber is introduced into the air, the plated substrate can be taken out.

如此所處理的基質的反射光譜在平均反射層度80%造成顏色座標L＊ 、＝94.3、a＊ ＝－1.8及b＊ ＝1.5，其中在波長400~700奈米得到一算術平均值。該層由數條膠帶拉離物(Abzug)構成，在一種Tesa 4124－包裝室的場合。在一先前的格段沒有層撕離現象，且用1% NaOH溶液作作用30分，用30分沒有可見的損壞。The reflection spectrum of the substrate thus treated resulted in color coordinates L * , =94.3, a * =-1.8 and b * =1.5 at an average reflection layer of 80%, wherein an arithmetic mean was obtained at a wavelength of 400 to 700 nm. This layer consists of several tape pulls (Abzug) in the case of a Tesa 4124-packaging room. There was no layer tear-off in a previous segment and 30 minutes with 1% NaOH solution, with no visible damage at 30 minutes.

在圖3中顯示一個施在一厚約3mm的聚羧酸酯板上的層系統的光譜反射程度，係對於由一硬層及一中間層構成的上層構造的不同層厚度在400奈米~700奈米之間的波長範圍的情形，測量作用利用X－Rite公司的一光譜光度計SP60對於D65照明及一2∘觀看者所作。金屬層由用磁子濺鍍的鋁構成，層厚度100奈米。此層系統利用上述方法製造，上中間層為10奈米。In Figure 3, the degree of spectral reflectance of a layer system applied to a polycarboxylate plate having a thickness of about 3 mm is shown. The thickness of the layer of the upper layer composed of a hard layer and an intermediate layer is 400 nm. In the case of a wavelength range between 700 nm, the measurement was performed using a spectrophotometer SP60 from X-Rite for D65 illumination and a 2 ∘ viewer. The metal layer is composed of aluminum sputtered with magnetic particles and has a layer thickness of 100 nm. This layer system was fabricated using the above method with an upper intermediate layer of 10 nm.

由圖3可看出，在整個所看的波長範圍，該未保護的金屬層的反射層度(亦即蓋層厚度為0)為最大。當蓋層厚度40奈米時，在短波長時已可發現反射程度有破壞(Einbruch)。當蓋層的厚度進一步增加時，可看到反射程度向較大波長減少。當層厚度160奈米時，在450~600奈米間的平均波長範圍可看到反射程度增加，當層厚度180奈米時，反射程度再向較短波長急遽下降。As can be seen from Figure 3, the reflective layer of the unprotected metal layer (i.e., the thickness of the cap layer is 0) is maximized throughout the wavelength range seen. When the thickness of the cap layer is 40 nm, it is found that the degree of reflection is broken at a short wavelength (Einbruch). As the thickness of the cap layer is further increased, it can be seen that the degree of reflection decreases toward a larger wavelength. When the layer thickness is 160 nm, the degree of reflection increases in the average wavelength range between 450 and 600 nm. When the layer thickness is 180 nm, the degree of reflection drops sharply toward the shorter wavelength.

在表1中顯示對於CIE L＊ a＊ b＊ 顏色印象、△E＊ 以及平均 反射程度(相對於入射光的%)的數值。此外，在一欄「注意」中放入主觀顏印象的評估中。此層厚度160奈米的層系統有一最大反射層度及一△E＊ <1.4。我們可看出固然在蓋層180奈米時發生較高亮度，但有黃色之顏色印象。The values for the CIE L * a * b * color impression, ΔE *, and the average degree of reflection (% relative to incident light) are shown in Table 1. In addition, an assessment of the subjective impression is placed in a column of "Attention". This layer system having a thickness of 160 nm has a maximum reflection layer and a ΔE * <1.4. We can see that although the brightness is higher at the cover layer of 180 nm, there is a yellow color impression.

(10)‧‧‧基質(10) ‧‧‧Matrix

(20)‧‧‧金屬層(20) ‧‧‧metal layer

(30)‧‧‧蓋層(30) ‧ ‧ cover

(40)‧‧‧上中間層(40) ‧‧‧ upper middle layer

(50)‧‧‧底層(50) ‧‧‧ bottom

(60)‧‧‧下中間層(60) ‧‧‧ lower middle layer

圖1係一本發明的層系統的示意圖，圖2係一與層厚度有關的反射程度的示圖，圖3係對不同之層厚度之一反射程度對反射光之波長之座標圖，此反射層度係施有一層系統的基質之所測量之反射程度。1 is a schematic view of a layer system of the present invention, FIG. 2 is a diagram showing the degree of reflection in relation to the thickness of the layer, and FIG. 3 is a graph showing the degree of reflection of the thickness of one of the different layers versus the wavelength of the reflected light. The degree of reflection is the degree of reflection measured by a system of substrates.

Claims (16)

一種在一基質上的耐擦拭的反射器用的層系統，包含一個光學反射金屬層和一個在該基質上在金屬層相反側的透明上層構造，該層構造具有一蓋層，由一電漿輔助析出的硬層構成，該硬層係以至少一種矽有機化合物為基礎者，且該層構造還可具有至少一中間層，其特徵在：該上層構造的層厚度選設成使得和該上層構造的層厚度有關的光譜平均反射程度有一最大值Rmax，和該上層構造的層厚度有關的反射程度的光譜平均值Rs的值>Rmetal-1/3△R，其中Rmetal係為該金屬層之未受到該蓋層保護的區域之一個類似於Rs測定的反射程度的一個類似於Rs所形成的光譜平均值，而△R=Rmetal-Rmin，且Rmin表示該與上層構造的層厚度有關的反射程度的最小值，或者在該與上層構造的層厚度有關的顏色印象Fs=(L* s,a* s,b* s)與該未受保護的金屬層的顏色印象Fm=(L* m,a* m,b* m)之間有一段顏色間隔△E*= <2.0。 A layer system for a wipe resistant reflector on a substrate comprising an optically reflective metal layer and a transparent upper layer structure on the substrate opposite the metal layer, the layer construction having a cap layer assisted by a plasma a precipitated hard layer composition based on at least one cerium organic compound, and the layer structure may further have at least one intermediate layer, characterized in that the layer thickness of the upper layer structure is selected such that the upper layer structure The average spectral reflectance of the layer thickness has a maximum value R max , and the value of the spectral mean value R s of the degree of reflection related to the layer thickness of the upper layer structure is > R metal - 1/3 ΔR, where R metal is the A region of the metal layer that is not protected by the cap layer is similar to the spectral average of R s measured by R s , and ΔR = R metal - R min , and R min represents the sum a minimum of the degree of reflection associated with the layer thickness of the superstructure, or a color impression F s = (L * s , a * s , b * s ) associated with the layer thickness of the superstructure and the unprotected metal layer Color impression F m = (L * m , a There is a color interval between * m , b * m ) △E * = <2.0. 如申請專利範圍第1項之層系統，其中：在該金屬層之朝向基質的那一側上在該金屬層與基質間設有一底層。 The layer system of claim 1, wherein a bottom layer is disposed between the metal layer and the substrate on a side of the metal layer facing the substrate. 如申請專利範圍第2項之層系統，其中：該底層為一受電漿輔助析出的(且宜為厚的)層，它基於至少一種矽有機化合物為基礎或為一種(宜為硬的) 漆層。 The layer system of claim 2, wherein: the bottom layer is a plasma-assisted (and preferably thick) layer based on at least one cerium organic compound or one (preferably hard) Paint layer. 如申請專利範圍第1或第2項之層系統，其中：在該蓋層與金屬層之間至少設有一上中間層。 The layer system of claim 1 or 2, wherein at least an upper intermediate layer is disposed between the cover layer and the metal layer. 如申請專利範圍第2項之層系統，其中：在該底層與金屬層之間至少設有一附加之下中間層。 The layer system of claim 2, wherein at least one additional lower intermediate layer is disposed between the bottom layer and the metal layer. 如申請專利範圍第1或第2項之層系統，其中：設有一下中間層及/或上中間層，具有防護氧以保護該金屬層。 The layer system of claim 1 or 2, wherein: the intermediate layer and/or the upper intermediate layer are provided with protective oxygen to protect the metal layer. 如申請專利範圍第1或第2項之層系統，其中：該矽有機化合物為六甲基二矽氧烷或四甲基二矽氧烷。 The layer system of claim 1 or 2, wherein the bismuth organic compound is hexamethyldioxane or tetramethyldioxane. 如申請專利範圍第1或第2項之層系統，其中：氧及/或氮儲在至少一硬層中。 A layer system of claim 1 or 2, wherein: oxygen and/or nitrogen are stored in at least one hard layer. 如申請專利範圍第8項之層系統，其中：該金屬層包含至少一夥伴成份，由鋁、銅、銀、金、鈦、鎂、鐵、鋼、鉻選出或由這些金屬所形成的合金選出。 The layer system of claim 8, wherein the metal layer comprises at least one partner component selected from aluminum, copper, silver, gold, titanium, magnesium, iron, steel, chromium or an alloy formed of the metals. . 如申請專利範圍第1或第2項之層系統，其中：該上層構造的層厚度在110奈米與200奈米之間的範圍。 A layer system according to claim 1 or 2, wherein the layer thickness of the upper layer structure is in the range between 110 nm and 200 nm. 一種在一基質上製造耐擦拭之光學反層器用的層系統的方法，其中在金屬層之與該基質相反的那一側上將一透明之上層構造施到一光學上反射的金屬層上，該透明上層構造具有一蓋層及至少一中間層，該蓋層由一受電漿輔助析出的硬層構成，以至少一種矽有機化合物為基礎， 其特徵在：該上層構造的層厚度選設成使得一與該上層構造的層厚度有關的光譜平均反射程度Rs有一最大值Rmax，且和該上層構造的層厚度有關的反射程度的光譜平均值Rs的值>Rmetal-1/3△R，其中Rmetal係為該金屬層之未受到該蓋層保護的區域之一個類似於Rs測定的反射程度的一個類似於Rs所形成的光譜平均值，而△R=Rmetal-Rmin，且Rmin表示該與上層構造的層厚度有關的反射程度的最小值，或者在該與上層構造的層厚度有關的顏色印象Fs=(L* s,a* s,b* s)與該未受保護的金屬層的顏色印象Fm=(L* m,a* m,b* m)之間有一段顏色間隔△E*= <2.0。 A method of fabricating a layer system for a wiping resistant optical reverse layer on a substrate, wherein a transparent upper layer structure is applied to an optically reflective metal layer on a side of the metal layer opposite the substrate, The transparent upper layer structure has a cap layer and at least one intermediate layer. The cap layer is composed of a hard layer which is supported by a plasma, and is based on at least one cerium organic compound, and is characterized in that the layer thickness of the upper layer structure is selected as The spectral average reflection degree R s relating to the layer thickness of the upper layer structure has a maximum value R max , and the value of the spectral average value R s of the degree of reflection relating to the layer thickness of the upper layer structure is >R metal -1/3 ΔR, wherein R metal is a spectral average value similar to R s formed by R s measured in a region of the metal layer not protected by the cap layer, and ΔR = R metal - R min , and R min represents the minimum value of the degree of reflection associated with the layer thickness of the superstructure, or the color impression F s =(L * s , a * s , b * s in relation to the layer thickness of the superstructure) ) and the unprotected metal layer Between the color impression F m = (L * m, a * m, b * m) for some interval △ E * = Color <2.0. 如申請專利範圍第11項之方法，其中：一股真空在製造層系統時保持不中斷。 The method of claim 11, wherein: a vacuum is maintained without interruption during the manufacture of the layer system. 如申請專利範圍第11或12項之方法，其中：該金屬層利用一濺鍍方法、物理或化學蒸鍍方法或一離子束方法施加。 The method of claim 11 or 12, wherein the metal layer is applied by a sputtering method, a physical or chemical vapor deposition method or an ion beam method. 如申請專利範圍第11項之方法，其中：該矽有機化合物為六甲二矽氧烷或四甲基二矽氧烷，其中在製造該蓋層時，將一反應性成分如氧及/或氮供應。 The method of claim 11, wherein the hydrazine organic compound is hexamethyldioxane or tetramethyldioxane, wherein a reactive component such as oxygen and/or nitrogen is used in the production of the cap layer. supply. 如申請專利範圍第14項之方法，其中：該反應性成分以六甲基二矽氧烷或四甲基二矽氧烷對該反應性成分的流率比例1：0.5到1：20供應。 The method of claim 14, wherein the reactive component is supplied in a flow ratio of 1:0.5 to 1:20 of hexamethyldioxane or tetramethyldioxane to the reactive component. 如申請專利範圍第11項之方法，其中： 施一上層構造，其層厚度在110奈米~200奈米範圍。For example, the method of claim 11 of the patent scope, wherein: Apply an upper layer structure with a layer thickness ranging from 110 nm to 200 nm.
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