JPH0234331A - Selective light-transmitting mica - Google Patents
Selective light-transmitting micaInfo
- Publication number
- JPH0234331A JPH0234331A JP18488888A JP18488888A JPH0234331A JP H0234331 A JPH0234331 A JP H0234331A JP 18488888 A JP18488888 A JP 18488888A JP 18488888 A JP18488888 A JP 18488888A JP H0234331 A JPH0234331 A JP H0234331A
- Authority
- JP
- Japan
- Prior art keywords
- mica
- film
- selective light
- transmitting
- onto
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052618 mica group Inorganic materials 0.000 title claims abstract description 57
- 239000010445 mica Substances 0.000 title claims abstract description 56
- 239000010408 film Substances 0.000 abstract description 31
- 239000010409 thin film Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007493 shaping process Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 8
- 229910052627 muscovite Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910003087 TiOx Inorganic materials 0.000 description 2
- 229910052626 biotite Inorganic materials 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229910052628 phlogopite Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- -1 K 2 ions Chemical class 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は1選択光透過性を存する雲母に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to mica that exhibits one-selective light transmission.
〔従来技術]
雲母は、天然に生産される鉱物で、一般に透明な物質で
ある。また、雲母は後述するごとく、正四面体からなる
層構造物質であるため、C軸方向の薄膜化が容易である
という特性を有する。そこで、この粉砕物は、化粧品、
塗料等に添加して。[Prior Art] Mica is a naturally produced mineral and is generally a transparent substance. Furthermore, as will be described later, mica is a layered material consisting of regular tetrahedrons, so it has the characteristic that it can be easily formed into a thin film in the C-axis direction. Therefore, this crushed material can be used for cosmetics,
Add to paint etc.
真珠光沢調を付与すること等に用いられる。It is used to impart a pearlescent tone.
また、近年においては、TiOア (二酸化チタン)な
ど屈折率の大きい金属酸化物の薄膜を表面にコーティン
グした雲母も提案されている。このものは、可視光と赤
外光を透過し、紫外光をカットする効果を有する。その
ため、このものは化粧品中に入れて日焼防止クリームと
して用いることができる。Furthermore, in recent years, mica whose surface is coated with a thin film of a metal oxide having a high refractive index such as TiO (titanium dioxide) has also been proposed. This material has the effect of transmitting visible light and infrared light and cutting off ultraviolet light. Therefore, this product can be incorporated into cosmetics and used as a sunscreen cream.
しかしながら1日焼防止クリームのみならず。 However, it is not limited to sun protection cream.
透明樹脂、サングラス等においては、紫外光と共に赤外
光も遮断したいという要望がある。In transparent resins, sunglasses, and the like, there is a desire to block infrared light as well as ultraviolet light.
本発明は、かかる従来の問題点に鑑み、前記特性を有す
る雲母を利用することに着目し、可視光は透過するが赤
外光及び紫外光は遮断することができる選択光透過性の
雲母を提供しようとするものである。In view of such conventional problems, the present invention focuses on the use of mica having the above-mentioned characteristics, and uses selective light-transmitting mica that can transmit visible light but block infrared light and ultraviolet light. This is what we are trying to provide.
本発明は、透明性を有する雲母の表面に2選択光透過膜
を形成してなることを特徴とする選択光透過性雲母にあ
る。The present invention resides in a selective light transmitting mica characterized by forming a two selective light transmitting film on the surface of transparent mica.
本発明において用いる雲母は、可視光透過性が90%以
上である。透明性を存するものを用いることが好ましい
。また、雲母は次に示す種類、特性を有する。即ち、雲
母の種類として最も一般的なものは、 (Aj!S
i、 Of。)S−の組成を持ち。The mica used in the present invention has a visible light transmittance of 90% or more. It is preferable to use a material that is transparent. Furthermore, mica has the following types and characteristics. That is, the most common type of mica is (Aj!S
i, Of. ) has the composition S-.
このStのうち1/4がAffiで置換されたものが白
雲母である。この白雲母は、5iOnの単位のうち成る
部分はA/!O,四面体に置換されていて。Muscovite is one in which 1/4 of this St is substituted with Affi. This muscovite has a unit of 5iOn that consists of A/! O, substituted with a tetrahedron.
2枚の層が四面体の頂点を内側に向けるようにしてAl
”+イオンで結ばれ、AN−自身はOH−イオンを使っ
て、六回体位を完成している。したがって、 CAI
tt (AffiSia O,。)(OH)i)の組
成をもって2枚の層が交互に積み重なり。Al
” Connected by + ions, AN- itself uses OH- ions to complete the six positions. Therefore, CAI
Two layers are stacked alternately with a composition of tt (AffiSia O,.)(OH)i).
電気的中性を保つために適当な数のK イオンが間に入
る。An appropriate number of K ions are interposed to maintain electrical neutrality.
雲母類はすべて単斜晶系で、底面を完全へき開面とし六
角板状である。白雲母、金雲母は無色または淡色、黒雲
母は濃色を示す、また、雲母は複屈折性が強く真珠また
は金属光沢を呈する。All micas are monoclinic and have a hexagonal plate shape with a completely cleaved base. Muscovite and phlogopite are colorless or light-colored, and biotite is dark-colored, and mica has strong birefringence and exhibits pearly or metallic luster.
雲母において上記へき開性が著しいのは、前記K イオ
ンの層にそった結合が弱いためである。The reason why the above-mentioned cleavability of mica is remarkable is that the bonds of the K 2 ions along the layer are weak.
一方1層の結合を役目をしているA2はMgに。On the other hand, A2, which acts as a bond in the first layer, is Mg.
サンドインチの間にあるKはNaに置き換わったり1種
々の類似構造ができ易い、このため、白雲母の他に、黒
雲母K (Mg、 F e) 3 (Aj!S +
、0.。)・ (OH)、z、金雲母K M g s
(A I 5iOue) ・ (OH)z 、更に
は鉄雲母、ソーダ雲母、鱗雲母、チンワルド雲母等が存
在する。K between the sand inches is easily replaced by Na or various similar structures are formed. Therefore, in addition to muscovite, biotite K (Mg, Fe) 3 (Aj!S +
, 0. . )・(OH), z, phlogopite K M g s
(A I 5i Oue) · (OH)z, and furthermore, iron mica, soda mica, lepidolite, Chinwald mica, etc. are present.
また、雲母は大きいもので直径201位のものも、天然
品等で入手することができる。かかる大板状の雲母を用
いた本発明の選択光透過性雲母は。In addition, large mica with a diameter of about 201 cm can be obtained as a natural product. The selective light transmitting mica of the present invention uses such large plate-like mica.
そのまま化学装置等ののぞき窓、建築物等の小窓などに
用いることができる。It can be used as is for viewing windows in chemical equipment, small windows in buildings, etc.
次に、雲母の表面に形成させる選択光透過膜としては、
可視光は透過させるが赤外光及び紫外光は殆ど透過させ
ない薄膜を用いる。Next, as a selective light transmission film to be formed on the surface of mica,
A thin film is used that transmits visible light but hardly transmits infrared and ultraviolet light.
かかる選択光透過膜としては2例えば金属薄膜の片面又
は両面に透明高屈折率酸化物を被覆した積層体を用いる
。As such a selective light transmitting film, for example, a laminate in which one or both sides of a metal thin film is coated with a transparent high refractive index oxide is used.
即ち、雲母の表面に透明高屈折率酸化物、金属薄膜、透
明高屈折率酸化物の順の三層からなる選択光透過膜、或
いは雲母の表面に透明高屈折率酸化物、金属薄膜の順の
二層、又は金属薄膜、透明高屈折率酸化物の順の二層か
らなる選択光透過膜を形成する。また、上記選択光透過
膜は雲母の片面又は両面に形成する。That is, a selective light transmission film consisting of three layers in the order of a transparent high refractive index oxide, a metal thin film, and a transparent high refractive index oxide on the surface of mica, or a transparent high refractive index oxide and a metal thin film on the mica surface in this order. or a metal thin film and a transparent high refractive index oxide in this order. Further, the selective light transmission film is formed on one or both sides of the mica.
上記金属薄膜としては、可視光領域の吸収損失が小さい
金、 銀、 w4.パラジウム及びこれらの合金が好ま
しい、金属薄膜の膜厚は1選択光透過膜としての要求を
満たすものであれば特に限定されるものではないが、透
明性を生かそうとすれば250Å以下が望ましい、また
、下限としては連続膜となり得る50Å以上が望ましい
。The metal thin film may include gold, silver, w4., which has low absorption loss in the visible light region. Palladium and alloys thereof are preferred. The thickness of the metal thin film is not particularly limited as long as it satisfies the requirements as a selective light transmitting film, but if transparency is to be utilized, it is preferably 250 Å or less. Further, the lower limit is preferably 50 Å or more so that a continuous film can be formed.
金属薄膜層を形成する方法としては、真空蒸着。Vacuum deposition is a method for forming a metal thin film layer.
スパッタリング等の乾式めっき法が適しているが。Dry plating methods such as sputtering are suitable.
該金属薄膜の上に透明高屈折率酸化物を形成さ遥る場合
には、スパッタリングが最も適している。When a transparent high refractive index oxide is to be formed on the metal thin film, sputtering is most suitable.
この金属薄膜は、雲母の表面に形成した透明高屈折率酸
化物の上、又は雲母の表面に形成させる。This metal thin film is formed on the transparent high refractive index oxide formed on the mica surface or on the mica surface.
金属薄膜の片面又は両面に設ける透明高屈折率酸化物は
、可視光に対する屈折率が1.8以上。The transparent high refractive index oxide provided on one or both sides of the metal thin film has a refractive index of 1.8 or more for visible light.
好ましくは2.0以上を存し、可視光透過率が80%以
上、好ましくは90%以上のものを用いる。It is preferably 2.0 or more and has a visible light transmittance of 80% or more, preferably 90% or more.
そして、その膜厚は、所望の選択光透過膜が得られるも
のであればよいが1通常は100〜600人、好ましく
は150〜400人である。しかして、これらの条件を
満たすものとしては、酸化チタン、硫化亜鉛、チタン酸
バリウムなどがある。The film thickness may be any thickness as long as a desired selective light transmitting film can be obtained, but it is usually 100 to 600, preferably 150 to 400. Examples of materials that meet these conditions include titanium oxide, zinc sulfide, and barium titanate.
透明高屈折率酸化物の形成法についても、前記金属薄膜
の形成法と同様であり、スパッタリングが好ましい。The method for forming the transparent high refractive index oxide is also the same as the method for forming the metal thin film, and sputtering is preferred.
本発明の選択光透過性雲母は、樹脂、ガラス等に混合し
たり、またそのまま窓等として1種々の態様で用いるこ
とができる。The selective light-transmitting mica of the present invention can be mixed with resins, glass, etc., or can be used as it is in various forms such as windows.
本発明の選択光透過性雲母は、雲母の表面に選択光透過
膜を形成してなる。そして、雲母は透明性を有し、かつ
複屈折性の大きい材料である。そのため、雲母の複屈折
性と5選択光透過膜の可視光選択性との特性により、真
珠光沢性を有すると共に、可視光は透過するが赤外光及
び紫外光は遮断することができる選択光透過性雲母を提
供することができる。The selective light transmitting mica of the present invention is formed by forming a selective light transmitting film on the surface of mica. Mica is a material that is transparent and has high birefringence. Therefore, due to the characteristics of the birefringence of mica and the visible light selectivity of the 5-selective light transmission film, it has pearlescent properties and can transmit visible light but block infrared and ultraviolet light. A transparent mica can be provided.
また、無機物である雲母を基材としているので耐熱性に
も優れている。また、天然物の雲母を基材とすることも
でき、安価である。更に、雲母として白雲母を用いた場
合には、白雲母は大きい複屈折性を有するので、非常に
優れた選択光透過性雲母とすることができる。Additionally, since the base material is mica, which is an inorganic material, it has excellent heat resistance. Furthermore, it is possible to use mica as a base material, which is a natural product, and is inexpensive. Furthermore, when muscovite is used as the mica, since muscovite has a large birefringence, it can be made into a mica with very excellent selective light transmission.
第1図に示すごとく、基材としての雲母1の片面の表面
に選択光透過膜2を形成した選択光透過性雲母を作製し
た。As shown in FIG. 1, selective light transmitting mica was prepared by forming a selective light transmitting film 2 on one surface of mica 1 as a base material.
上記選択光透過l!!2は、雲母1の表面に透明高屈折
率酸化物としてのTi1t膜21.その上に金属薄膜と
してのAg1l1122.更に最上面に透明高屈折率酸
化物としてのTi01膜21を形成したものである。The above selected light transmission l! ! 2 is a TiIt film 21.2 as a transparent high refractive index oxide on the surface of the mica 1. On top of that, Ag1l1122 as a metal thin film. Furthermore, a Ti01 film 21 as a transparent high refractive index oxide is formed on the uppermost surface.
上記雲母lとしては、30X50■、厚み200μmの
薄片状の白雲母を用いた0次いで、イソプロピルアルコ
ールにより、該雲母のベースコート塗膜の表面を脱脂し
た後、アルゴン(A r )ガス7X 10−’To
r r雰囲気中で基板エンチングを行った。この時の出
力は150Wでエツチング時間は20分であった。As the above mica, flaky muscovite having a size of 30×50 mm and a thickness of 200 μm was used.Next, the surface of the base coat film of the mica was degreased with isopropyl alcohol, and then argon (Ar) gas 7×10−' was used. To
The substrate was etched in an r r atmosphere. The output at this time was 150 W and the etching time was 20 minutes.
次に、上記選択光透過膜2を形成するに当り。Next, in forming the selective light transmitting film 2.
まず下層の透明高屈折率酸化物としてのT i Oz膜
21形成のため、銅プレートにメタルボンディングした
T i Oz ターゲット(純度99.99%)を用
い、高周波利用のRFマグネトロンスパッタ装置にて、
RF出力600W、Ar圧7×10−’Torrで、3
50人の透明高屈折率酸化物としてのT i Ox M
21を雲母上に形成した。First, in order to form the T i Oz film 21 as the lower layer transparent high refractive index oxide, a T i Oz target (purity 99.99%) metal-bonded to a copper plate is used, and an RF magnetron sputtering device using high frequency is used.
RF output 600W, Ar pressure 7×10-'Torr, 3
50 T i Ox M as transparent high refractive index oxides
21 was formed on mica.
次いで、金属薄膜としてのAg膜22形成のためAgタ
ーゲット(99,99%)を用い、DC(直流)出力0
.5AX550Vt’lOO人の金属薄膜としてのAg
膜22を形成した。その後。Next, an Ag target (99,99%) was used to form the Ag film 22 as a metal thin film, and a DC (direct current) output of 0 was used.
.. 5AX550Vt'lOOAg as a human metal thin film
A film 22 was formed. after that.
更に最上層の透明高屈折率酸化物形成のため、上記下層
のT i Ox Wf121と同じ条件でAg膜22上
に上層のTiOx膜21を300人形成した。Furthermore, in order to form a transparent high refractive index oxide as the uppermost layer, 300 people formed the upper TiOx film 21 on the Ag film 22 under the same conditions as the lower layer TiOx Wf121.
以上により0本例にかかる選択光透過性雲母を得た。As described above, selective light transmitting mica according to Example 0 was obtained.
得られた選択光透過性雲母(本発明品)について、その
光透過率を300〜2500nmの波長領域において、
測定した。その結果を、第2図に横軸に波長(nm)を
、継軸に光透過率(%)をとって示す。第2図より知ら
れるごとく2本発明品は、可視光領域において70%程
度の透過率を示すが、赤外光及び紫外光の透過率は非常
に低いことが分る。The light transmittance of the obtained selective light transmitting mica (product of the present invention) was determined in the wavelength range of 300 to 2500 nm.
It was measured. The results are shown in FIG. 2, with wavelength (nm) plotted on the horizontal axis and light transmittance (%) plotted on the joint axis. As can be seen from FIG. 2, the two products of the present invention exhibit a transmittance of about 70% in the visible light region, but the transmittance of infrared light and ultraviolet light is extremely low.
これに対し、前記本発明品において選択光透過膜を形成
していない白雲母のみについても測定した。その結果、
同図に示すごとく、可視光、赤外光いずれの領域におい
ても高い光透過性を示し。On the other hand, in the product of the present invention, only the muscovite on which the selective light transmission film was not formed was also measured. the result,
As shown in the figure, it exhibits high light transmittance in both visible light and infrared light regions.
選択光透過性を有していないことが分る。It can be seen that it does not have selective light transmittance.
図は実施例を示し、第1図は選択光透過性雲母の説明断
面図、第2図は選択光透過性雲母の光透過率を示す線図
である。
22、、、Ag膜。The figures show examples; FIG. 1 is an explanatory cross-sectional view of selectively transparent mica, and FIG. 2 is a diagram showing the light transmittance of selectively transparent mica. 22, Ag film.
Claims (1)
なることを特徴とする選択光透過性雲母。1. A selectively light-transmitting mica, characterized in that a selective light-transmitting film is formed on the surface of transparent mica.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18488888A JPH0234331A (en) | 1988-07-25 | 1988-07-25 | Selective light-transmitting mica |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18488888A JPH0234331A (en) | 1988-07-25 | 1988-07-25 | Selective light-transmitting mica |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0234331A true JPH0234331A (en) | 1990-02-05 |
Family
ID=16161072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18488888A Pending JPH0234331A (en) | 1988-07-25 | 1988-07-25 | Selective light-transmitting mica |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0234331A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999031023A1 (en) * | 1997-12-17 | 1999-06-24 | Merck Patent Gmbh | Transparent medium with angular-selective transmitting or reflecting properties |
-
1988
- 1988-07-25 JP JP18488888A patent/JPH0234331A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999031023A1 (en) * | 1997-12-17 | 1999-06-24 | Merck Patent Gmbh | Transparent medium with angular-selective transmitting or reflecting properties |
US6602340B1 (en) | 1997-12-17 | 2003-08-05 | Merck Patent Gmbh | Transparent medium with angular-selective transmitting or reflecting properties |
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