JP2004078090A - Reflecting mirror - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new reflecting mirror with a layer including one or more matters selected from a group consisting of silicon, titanium, germanium, selenium and tellurium in place of the conventional silicon oxide layer between a glass substrate and a layer including aluminum and/or silver and to provide its manufacturing method. <P>SOLUTION: In this reflecting mirror provided with the layer (II) mainly including aluminum and/or silver on the glass substrate, there is the layer (I) mainly including one or more matters to be selected from a group consisting of silicon, titanium, germanium, selenium and tellurium between the glass substrate and the layer (II). <P>COPYRIGHT: (C)2004,JPO

Description

【００２６】
表１における各評価試験の方法及び評価の基準は下記の通りである。
【００２７】
＜チーズクロス試験＞
ＭＩＬ−Ｍ−１３５０８Ｃに準拠し、６８０ｇ／ｃｍ^２の荷重をかけて５０回往復して反射鏡表面上のキズの有無を調べた。
○：表面にキズなし
×：表面に多数のキズあり
【００２８】
＜スチールウール試験＞
スチールウール（日本スチールウール株式会社製、ボンスターＮｏ．００００（商標）を使用して、１０００ｇ／ｃｍ^２で反射鏡表面上を１０往復してキズの有無を調べた。
○：表面にキズなし
Δ：表面に若干のキズあり
×：表面に多数のキズあり
【００２９】
＜テープ剥離試験＞
ＭＩＬ−Ｃ−４８４９７Ａに準拠し、３Ｍ　Ｎｏ．６１０のテープを使用してアルミニウム層の剥離の有無を調べた。
○：剥離なし
×：剥離あり
【００３０】
＜耐食性試験＞
ＭＩＬ−ＳＦＤ−８１０Ｆに準拠し、５％ＮａＣｌ水溶液を２４時間噴霧して表面劣化の有無を調べた。
○　：劣化なし
Δ：若干の劣化が見られた
×：激しい劣化が見られた
【００３１】
＜耐湿性試験＞
ＭＩＬ−Ｃ−４８４９７Ａに準拠し、相対湿度９５％、温度４９℃において２４時間曝して表面劣化の有無を調べた。
○　：劣化なし
×：激しい劣化が見られた
【００３２】
＜耐高温性試験＞
温度７０℃において８時間保持して表面劣化の有無を調べた。
○　：劣化なし
×：激しい劣化が見られた
【００３３】
【発明の効果】
本発明は、ガラス基板とアルミニウム及び／又は銀を含む層との間に、従来の酸化ケイ素層に代えて、ケイ素、チタン、ゲルマニウム、セレン及びテルルより成る群から選ばれる一つ以上の物質を含む層がある、新規な反射鏡及びその製造方法を提供するものである。
【図面の簡単な説明】
【図１】実施例で使用したスパッタリング装置の概略図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a reflector, and more particularly, to a multilayer reflector having a high reflectance.
[0002]
[Prior art]
Conventionally, in a reflecting mirror, an SiO ₂ layer is provided on a glass, plastic, or ceramic substrate, and a metal reflecting layer, such as aluminum or silver, is provided thereon (see JP-A-5-150105 and JP-A-5-150105). -281405). Thereby, corrosion of the metal reflection layer by the substrate can be prevented, and adhesion between the substrate and the metal reflection layer can be enhanced.
[0003]
JP-A-8-304614 discloses a silicon thin film layer formed on one surface of a predetermined synthetic resin optical member, and a gradient composition structure formed on the silicon thin film layer and having a gradually increasing oxygen compounding ratio. There is disclosed a synthetic resin reflector comprising: a silicon oxide thin film layer having: a metal reflective layer formed on the silicon oxide layer; and an oxide protective film layer formed on the metal reflective layer. ing. The reflecting mirror uses a synthetic resin, for example, a polycarbonate resin substrate. In addition, it is essential to provide a silicon oxide thin film layer between the substrate and the metal reflection layer as in the conventional case.
[0004]
[Problems to be solved by the invention]
The present invention provides one or more substances selected from the group consisting of silicon, titanium, germanium, selenium and tellurium between the glass substrate and the layer containing aluminum and / or silver, instead of the conventional silicon oxide layer. The present invention provides a novel mirror having a layer containing the same and a method for manufacturing the same.
[0005]
[Means for Solving the Problems]
In a conventional reflector, a silicon oxide layer is provided between the substrate and the reflective layer in order to prevent corrosion of the reflective layer by a substrate, for example, a glass substrate, and to enhance adhesion between the substrate and the reflective layer. Had been provided. The silicon oxide layer has almost no battery action between the substrate and the reflective layer, and hardly causes corrosion. The adhesion between the silicon oxide layer and the reflective layer was mainly maintained by the unevenness of the surface of each layer. The present inventors have investigated various substances that can be used in place of the conventional silicon oxide layer. As a result, when a layer of the following predetermined substance is used, the substance causes an intermetallic bond between the substrate and the reflective layer, and therefore, the above-mentioned conventional silicon oxide layer has excellent adhesion, and the following predetermined substance is used. Found that there was almost no battery action with the glass substrate and there was no corrosion.
[0006]
That is, the present invention
(1) In a reflector provided with a layer (II) mainly containing aluminum and / or silver on a glass substrate, a group consisting of silicon, titanium, germanium, selenium, and tellurium between the glass substrate and the layer (II). A reflector (I) mainly containing one or more substances selected from the group consisting of:
[0007]
As a preferred embodiment,
(2) The reflecting mirror according to the above (1), wherein the layer (II) is a layer mainly containing aluminum.
(3) The reflector according to (1) or (2), wherein the layer (I) is a layer mainly containing silicon or titanium.
(4) The reflecting mirror according to any one of the above (1) to (3), wherein the thickness of the layer (I) is 2 to 50 nm.
(5) The reflecting mirror according to any one of the above (1) to (3), wherein the thickness of the layer (I) is 10 to 30 nm,
(6) The reflecting mirror according to any one of the above (1) to (5), wherein the thickness of the layer (II) is 40 to 100 nm.
(7) The reflector according to any one of the above (1) to (5), wherein the thickness of the layer (II) is 60 to 80 nm,
(8) layer on the (II), further, a layer having a refractive index _{n 1} (III) layer and having a refractive index _{n 2} than _{n 1} (IV) is in the alternate place of (1) The reflecting mirror according to any one of (1) to (7),
(9) on the layer (II), further, a layer having a refractive index _{n 1} layer having a refractive index _{n 2} than (III) and _{n 1} (IV) is, where there is respectively fourth layers alternately The reflecting mirror according to any one of the above (1) to (7),
(10) on the layer (II), further, a layer having a refractive index _{n 1} layer having a refractive index _{n 2} than (III) and _{n 1} (IV) is, where there is respectively 2-4 layers alternately The reflecting mirror according to any one of the above (1) to (7),
(11) The reflecting mirror according to any one of the above (8) to (10), wherein the layer (III) is a layer mainly containing silicon dioxide or magnesium fluoride.
(12) The reflecting mirror according to any one of the above (8) to (11), wherein the layer (III) is a layer mainly containing silicon dioxide.
(13) The reflecting mirror according to any one of (8) to (12) above, wherein the layer (IV) is a layer mainly containing titanium dioxide, tantalum oxide, or zirconium oxide.
(14) The reflecting mirror according to any one of the above (8) to (12), wherein the layer (IV) is a layer mainly containing titanium dioxide.
(15) The reflector according to any one of the above (8) to (14), wherein the thickness of the layer (III) is 60 to 90 nm,
(16) The reflecting mirror according to any one of the above (8) to (14), wherein the thickness of the layer (III) is 70 to 80 nm.
(17) The reflecting mirror according to any one of the above (8) to (16), wherein the thickness of the layer (IV) is 30 to 60 nm.
(18) The reflecting mirror according to any one of the above (8) to (16), wherein the thickness of the layer (IV) is 40 to 50 nm.
(19) The method for producing a reflecting mirror according to any one of (1) to (18) above, wherein each of the above layers is applied by using sputtering.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The reflector according to the present invention is a reflector provided with a layer (II) mainly containing aluminum and / or silver on a glass substrate, wherein silicon, titanium, germanium, selenium, and silicon are interposed between the glass substrate and the layer (II). There is a layer (I) mainly containing one or more substances selected from the group consisting of tellurium.
[0009]
The layer (I) is a layer mainly containing one or more substances selected from the group consisting of silicon, titanium, germanium, selenium, and tellurium. Preferably, a layer mainly containing silicon or titanium is used. In the layer (I), the substance is preferably contained in an amount of 85% by weight or more, more preferably 90% by weight or more, still more preferably 99.0% by weight or more, particularly preferably 99.9 to 99.999% by weight. Other substances included in the layer (I) include aluminum, magnesium, manganese, iron, nickel, chromium (chromium nitride, chromium carbide), aluminum, gallium, and indium. For example, silicon containing 10% by weight of aluminum can be used. The layer (I) is provided between the glass substrate and the layer (II) to prevent the corrosion of the layer (II) by the glass substrate and to enhance the adhesion between the glass substrate and the layer (II) to remove the layer. It is to prevent. The thickness of the layer (I) is determined depending on the adhesion between the glass substrate and the layer (II) and the light resistance of the layer (II), and the upper limit is preferably 50 nm, more preferably 40 nm, and still more preferably 30 nm. Yes, the lower limit is preferably 2 nm, more preferably 5 nm, and still more preferably 10 nm. If the upper limit is exceeded, the surface smoothness of the film will be deteriorated, adversely affecting the film strength and the reflectance. If it is less than the lower limit, the adhesive force between the glass substrate and the layer (II) will be weak.
[0010]
The layer (II) mainly containing aluminum and / or silver functions as a reflective layer. Preferably, a layer mainly containing aluminum is used. In the layer (II), aluminum and / or silver is preferably contained in an amount of 99.0% by weight or more, more preferably 99.9 to 99.999% by weight. The thickness of the layer (II) is appropriately determined depending on the reflectance. The upper limit of the thickness is preferably 100 nm, more preferably 90 nm, and still more preferably 80 nm, and the lower limit is preferably 40 nm, more preferably 50 nm, and still more preferably 60 nm. If the upper limit is exceeded, the smoothness will be lost and the reflectance will decrease, and if it is less than the lower limit, the effect as a reflective layer will not be obtained.
[0011]
In the reflecting mirror of the present invention, on the layer (II), further, a layer having a refractive index n ₁ as a low refractive index layer (III), and having a large refractive index n ₂ than n ₁ as a high refractive index layer Preferably, the layers (IV) are alternating. As the number of the layers (III) and (IV) increases, the performance of the reflecting mirror improves, but from the viewpoint of economy, it is preferably 1 to 6 layers, more preferably 1 to 4 layers, and still more preferably 2 layers. ~ 4 layers.
[0012]
The layer (III) may be any layer as long as it is transparent and durable, and is preferably a layer mainly containing silicon dioxide or magnesium fluoride. More preferably, a layer mainly containing silicon dioxide is used. In the layer (III), the substance is preferably contained in an amount of 99% by weight or more, more preferably 99.9 to 99.999% by weight. On the other hand, the layer (IV) also needs to be transparent and durable, and is preferably a layer mainly containing titanium dioxide, tantalum oxide or zirconium oxide. More preferably, a layer mainly containing titanium dioxide is used. In the layer (IV), the substance is preferably contained in an amount of 99% by weight or more, more preferably 99.9 to 99.999% by weight.
[0013]
The layer (III) and the layer (IV) can be stacked in a predetermined number as described above to increase the reflectance. The upper limit of the thickness of each of the layer (III) and the layer (IV) is preferably 100 nm, more preferably 90 nm, and still more preferably 80 nm, and the lower limit is preferably 30 nm, more preferably 40 nm, further preferably 50 nm, particularly preferably 50 nm. Preferably it is 60 nm, even more preferably 70 nm. The reflectance can be optimized by adjusting the thickness of each film within the above range. Outside the above range, the reflectivity is remarkably reduced, which is not preferable.
[0014]
In the reflecting mirror of the present invention, a coat such as water repellency and hydrophilicity can be further applied on the layer (III) and the layer (IV) within a range that does not affect the reflectance. Also, the top layer of the reflector can be a layer of titanium dioxide, which can be made superhydrophilic.
[0015]
The glass substrate is not particularly limited, and may be any glass substrate that can be used for construction or general industry. The composition is not particularly limited, and glass substrates having various softening points such as commonly used soda-lime glass, borosilicate glass, and high-strength crystallized glass can be used. The glass substrate may be manufactured by any method known in the art. However, a float plate glass (mirror grade) formed on a metal that is not melted and melted due to the necessity of having no distortion in the plane portion of the reflector of the present invention. It is preferred to use The thickness, shape and dimensions of the glass substrate can be freely determined according to the purpose. In particular, a glass substrate having a large area, preferably 2.0 to 3.0 m long × 3.0 to 4.0 m wide, for example, 2.5 m long × 3.7 m wide can be used.
[0016]
There is no particular limitation on the method for manufacturing the reflector of the present invention. Preferably, the layer (I) mainly containing one or more substances selected from the group consisting of silicon, titanium, germanium, selenium and tellurium, the layer (II) mainly containing aluminum and / or silver, and if desired, the refractive index n ₁ layer (III) with a layer preferably containing mainly silicon dioxide or magnesium fluoride, and a layer having a large refractive index n ₂ than the n ₁ (IV), preferably titanium dioxide, tantalum oxide or zirconium oxide Manufactured by applying all the layers that are mainly contained using sputtering. It is preferable that the sputtering conditions for these layers be the same. The temperature of sputtering is preferably ambient temperature. The pressure in the vacuum chamber is preferably 0.01 to 3 Pa, more preferably 0.01 to 0.3 Pa. Thus, the application of each layer can be made into a stream line, and the application can be performed more easily and economically.
[0017]
The reflecting mirror of the present invention thus obtained is used, for example, for optical / reflecting materials such as electric / electronic products, home appliances, building materials, etc., and particularly, rear projection televisions, overhead projectors, scanners, and copiers. obtain.
[0018]
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[0019]
【Example】
Embodiment 1
As a glass substrate, a float plate glass mirror grade borosilicate glass was used. The dimensions of the glass substrate were 2.5 m in length, 3.7 m in width, and 3 mm in thickness.
[0020]
As the sputtering apparatus, a continuous type shown in FIG. 1 was used. Argon and oxygen were used as plasma generation gases. The sputtering temperature was the ambient temperature (about 15 ° C.), and the pressure in the vacuum chamber was 0.3 Pa. In the sputtering apparatus, the glass substrate moves on the conveyor along the product flow direction. A silicon layer (10 nm) is applied on the glass substrate in zone 1, an aluminum layer (60 nm) is applied on the silicon layer in zone 2, and a silicon dioxide layer (60 nm) is applied on the aluminum layer in zone 3. 75 nm) and finally in zone 4 a titanium dioxide layer (45 nm) on the silicon dioxide layer.
[0021]
The large-area reflecting mirror thus obtained was cut into a predetermined size to obtain a sample for performance evaluation.
[0022]
Embodiment 2
In zone 1, the procedure was as in example 1, except that a titanium layer (20 nm) was applied on the glass substrate instead of the silicon layer.
[0023]
[Comparative Example 1]
In zone 1, the procedure was the same as in example 1, except that nothing was applied on the glass substrate.
[0024]
Table 1 shows the above results.
[0025]
[Table 1]

[0026]
The methods and evaluation criteria for each evaluation test in Table 1 are as follows.
[0027]
<Cheesecloth test>
In accordance with MIL-M-13508C, a reciprocation was performed 50 times under a load of 680 g / cm ^{2 under} a load of 680 g / cm ² , and the presence or absence of scratches on the surface of the reflecting mirror was examined.
：: No scratches on the surface ×: Many scratches on the surface
<Steel wool test>
Using a steel wool (manufactured by Nippon Steel Wool Co., Ltd., Bonstar No. 0000 (trademark)), the surface of the reflector was reciprocated 10 times at 1,000 g / cm ² to check for the presence or absence of scratches.
：: No scratch on the surface Δ: Some scratches on the surface ×: Many scratches on the surface
<Tape peel test>
Based on MIL-C-48497A, 3M No. The presence or absence of peeling of the aluminum layer was examined using the tape of No. 610.
：: no peeling x: peeling occurred [0030]
<Corrosion resistance test>
In accordance with MIL-SFD-810F, a 5% aqueous NaCl solution was sprayed for 24 hours to check for surface deterioration.
: No deterioration Δ: slight deterioration was observed x: severe deterioration was observed
<Moisture resistance test>
In accordance with MIL-C-48497A, the film was exposed for 24 hours at a relative humidity of 95% and a temperature of 49 ° C., and the presence or absence of surface deterioration was examined.
：: no deterioration x: severe deterioration was observed
<High temperature resistance test>
It was kept at a temperature of 70 ° C. for 8 hours to check for surface deterioration.
：: no deterioration x: severe deterioration was observed [0033]
【The invention's effect】
The present invention provides one or more substances selected from the group consisting of silicon, titanium, germanium, selenium and tellurium between the glass substrate and the layer containing aluminum and / or silver, instead of the conventional silicon oxide layer. The present invention provides a novel mirror having a layer containing the same and a method for manufacturing the same.
[Brief description of the drawings]
FIG. 1 is a schematic view of a sputtering apparatus used in Examples.

Claims (4)

In a reflector provided with a layer (II) mainly containing aluminum and / or silver on a glass substrate, between the glass substrate and the layer (II), selected from the group consisting of silicon, titanium, germanium, selenium and tellurium. A reflector, characterized in that there is a layer (I) mainly comprising one or more substances. The reflector according to claim 1, wherein the thickness of the layer (I) is 2 to 50 nm. 3. The reflector according to claim 1, wherein the layer (II) further comprises, alternately, 1 to 4 layers (III) mainly containing silicon dioxide and (IV) layers mainly containing titanium dioxide. . The method for manufacturing a reflector according to any one of claims 1 to 3, wherein each of the layers is applied by sputtering.

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