JP5251365B2 - Near-infrared cut filter glass - Google Patents
Near-infrared cut filter glass Download PDFInfo
- Publication number
- JP5251365B2 JP5251365B2 JP2008219908A JP2008219908A JP5251365B2 JP 5251365 B2 JP5251365 B2 JP 5251365B2 JP 2008219908 A JP2008219908 A JP 2008219908A JP 2008219908 A JP2008219908 A JP 2008219908A JP 5251365 B2 JP5251365 B2 JP 5251365B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- infrared cut
- cut filter
- component
- chemical durability
- 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.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims description 73
- 238000012937 correction Methods 0.000 claims description 12
- 238000003384 imaging method Methods 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 description 18
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000005365 phosphate glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 206010040925 Skin striae Diseases 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000005303 fluorophosphate glass Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 238000001444 catalytic combustion detection Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Images
Landscapes
- Glass Compositions (AREA)
Description
本発明は、デジタルスチルカメラ（以下、ＤＳＣと称する）やカラービデオカメラなどの視感度補正フィルタ等に使用される、４００〜６００ｎｍの可視域を効率よく透過し、７００ｎｍ付近におけるシャープカット特性に優れた近赤外線カットフィルタガラスに関する。 The present invention efficiently transmits the visible region of 400 to 600 nm and is excellent in sharp cut characteristics in the vicinity of 700 nm, which are used in a visibility correction filter for digital still cameras (hereinafter referred to as DSC) and color video cameras. It relates to near infrared cut filter glass.
ＤＳＣやカラービデオカメラに使用されるＣＣＤやＣＭＯＳ等の固体撮像素子は、可視域から１１００ｎｍ付近の近赤外域にわたる分光感度を有している。従って、そのままでは良好な色再現性を得ることができないので、近赤外域を吸収するフィルタを用いて通常の視感度に補正することが必要である。 Solid-state imaging devices such as CCDs and CMOSs used in DSCs and color video cameras have spectral sensitivity ranging from the visible region to the near infrared region near 1100 nm. Therefore, since good color reproducibility cannot be obtained as it is, it is necessary to correct to normal visibility using a filter that absorbs the near infrared region.
従来、このフィルタには近赤外波長を選択的に吸収するようにリン酸塩系ガラスにＣｕＯを添加したガラスが使用されていた。このガラスは多量のＰ２Ｏ５と必須成分としてＣｕＯを含有しており、酸化性の溶融雰囲気で、多数の酸素イオンに配位されたＣｕ２＋イオンを形成させることによって青緑色を呈し、近赤外線カット特性を有するものである。 Conventionally, a glass obtained by adding CuO to a phosphate glass so as to selectively absorb near-infrared wavelengths has been used for this filter. This glass contains a large amount of P 2 O 5 and CuO as an essential component, and exhibits a blue-green color by forming Cu 2+ ions coordinated to a large number of oxygen ions in an oxidizing molten atmosphere. It has infrared cut characteristics.
しかし、リン酸塩系ガラスは、化学的耐久性（耐候性）が不十分なため、ガラス研磨面にウエザリングを生じるので長期間にわたって使用するには難点がある。また、近赤外線カット効果を促進するためにＣｕＯの含有量を増加させると、一般に４００〜５００ｎｍの波長域における分光透過性が低下して緑色化の傾向を示し、かつ６００〜７００ｎｍの波長におけるシャープカット性が悪化するという問題がある。 However, since phosphate glass has insufficient chemical durability (weather resistance), it causes weathering on the glass polished surface, and thus has a difficulty in using it over a long period of time. Further, when the content of CuO is increased in order to promote the near-infrared cut effect, the spectral transmittance generally decreases in the wavelength range of 400 to 500 nm, and tends to be green, and sharp at wavelengths of 600 to 700 nm. There is a problem that the cut property deteriorates.
このため、リン酸塩系ガラスの化学的耐久性の低さを改善するために基礎ガラスとしてフツリン酸塩系ガラスを用い、これにＣｕＯを添加したガラス、たとえば特開平１−２１９０３７号公報、特開平３−８３８３４号公報に記載のフツリン酸塩系ガラスなどが開発されている。 For this reason, in order to improve the low chemical durability of phosphate glass, fluorophosphate glass is used as a base glass, and CuO is added to this glass, for example, Japanese Patent Laid-Open No. 1-219037. The fluorophosphate glass described in Kaihei 3-83834 has been developed.
近年、屋外に常設される監視用カラーカメラや自動車の周囲状況を画像認識するための車載カメラなどの需要が増大している。これらのカメラは使用環境が苛酷であるため、搭載される近赤外線カットフィルタガラスには、ＤＳＣやカラービデオカメラに用いられるものに比べ、より高い耐候性が要求される。 In recent years, there has been an increasing demand for a color camera for monitoring that is permanently installed outdoors and an in-vehicle camera for recognizing an image of the surroundings of an automobile. Since these cameras are used in harsh environments, the near-infrared cut filter glass to be mounted is required to have higher weather resistance than those used for DSCs and color video cameras.
本発明は、このような事情を考慮してなされたもので、化学的耐久性に非常に優れ、かつ４００ｎｍ付近の波長域を効率よく透過する近赤外線カットフィルタガラスを提供することを目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a near-infrared cut filter glass that is extremely excellent in chemical durability and efficiently transmits a wavelength region near 400 nm. .
上記目的を達成するため、本発明の近赤外線カットフィルタガラスは、カチオン％表示で、Ｐ５＋ ３５〜７５％、Ａｌ３＋ ０．２〜２０％、Ｒ１ ＋ ０〜１６．６％（ただし、Ｒ１ ＋はＬｉ＋、Ｎａ＋及びＫ＋の合計量）、Ｒ２ ２＋ １〜３５％（ただし、Ｒ２ ２＋はＭｇ２＋、Ｃａ２＋、Ｓｒ２＋及びＢａ２＋の合計量）、Ｓｂ３＋ ２〜１０％、Ｃｕ２＋ ０．５〜１３％を含むとともに、アニオン成分として、アニオン％表示で、Ｆ− １０〜４５％及びＯ２− ５５〜９０％を含むことを特徴とする。 To achieve the above object, the near-infrared cut filter glass of the present invention, by cationic%, P 5+ 35~75%, Al 3+ 0.2~20%, R 1 + 0~ 16.6% ( provided that R 1 + is the total amount of Li + , Na + and K + ), R 2 2+ to 35% (where R 2 2+ is the total amount of Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ ), Sb 3+ 2 10%, with including Cu 2+ 0.5 to 13%, as an anion component, an anion percentages, F - characterized in that it comprises a 10 to 45% and O 2-55 to 90%.
さらに、本発明は、上記近赤外線カットフィルタガラスを用いた固体撮像素子用視感度補正フィルタであることを特徴とする。 Furthermore, the present invention is a visibility correction filter for a solid-state imaging device using the near infrared cut filter glass.
本発明の近赤外線カットフィルタガラスは、化学的耐久性に非常に優れ、かつ４００ｎｍ付近の波長域を効率よく透過するため、例えば過酷な環境で使用される屋外常設の監視用カラーカメラや車載用カメラ等の固体撮像素子用視感度補正フィルタの近赤外線カットフィルタガラスとして好適に用いることができる。 The near-infrared cut filter glass of the present invention is very excellent in chemical durability and efficiently transmits a wavelength region near 400 nm. For example, it is used for outdoor surveillance color cameras for use in harsh environments and for in-vehicle use. It can be suitably used as a near-infrared cut filter glass for a visibility correction filter for a solid-state imaging device such as a camera.
本発明のガラスを構成する各成分の作用と、その組成範囲を上記のように限定した理由を説明する。以下の説明では、カチオン成分の含有量をカチオン％により表示し、アニオン成分の含有量をアニオン％により表示するものとする。なお、ここで、カチオン％及びアニオン％は、それぞれ原子％で示した値である。 The effect | action of each component which comprises the glass of this invention and the reason which limited the composition range as mentioned above are demonstrated. In the following description, the content of the cation component is represented by cation%, and the content of the anion component is represented by% anion. Here, the cation% and the anion% are values expressed in atomic%, respectively.
Ｐ５＋は、ガラスの網目構造を形成する主成分であるが、３５％未満ではガラスの安定性が悪くなり、また熱膨張係数が大きくなって耐熱衝撃性が低下する。７５％を超えると化学的耐久性が低下して長期使用におけるウエザリングが懸念される。好ましい範囲は４５〜６０％である。 P 5+ is a main component that forms a network structure of glass, but if it is less than 35%, the stability of the glass deteriorates, and the thermal expansion coefficient increases, resulting in a decrease in thermal shock resistance. If it exceeds 75%, the chemical durability is lowered and there is a concern about weathering in long-term use. A preferred range is 45-60%.
Ａｌ３＋は、ガラスの化学的耐久性を向上させ、ガラスの粘性を高める成分であるが、０．２％未満ではその効果が得られず、２０％を越えるとガラス化が困難となる。好ましい範囲は、５〜１５％である。 Al 3+ is a component that improves the chemical durability of the glass and increases the viscosity of the glass. However, if it is less than 0.2%, the effect cannot be obtained, and if it exceeds 20%, vitrification becomes difficult. A preferable range is 5 to 15%.
Ｒ２ ２＋（Ｒ２ ２＋は、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋及びＢａ２＋の合計量）は、ガラスの化学的耐久性を低下することなくガラスを安定するのに効果があるが、これらの合量が１％未満ではガラス化しにくく、３５％を超えるとガラス化が不安定となり、失透を生じやすくなるので好ましくない。好ましい範囲は、１０〜２０％である。また、各成分の好ましい範囲は、Ｍｇ２＋３〜２０％、Ｃａ２＋１〜１０％、Ｓｒ２＋２〜１０％、Ｂａ２＋２〜１０％である。 R 2 2+ (R 2 2+ is the total amount of Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ ) is effective in stabilizing the glass without reducing the chemical durability of the glass. If the total amount is less than 1%, it is difficult to vitrify, and if it exceeds 35%, vitrification becomes unstable and devitrification tends to occur, which is not preferable. A preferable range is 10 to 20%. Moreover, the preferable range of each component is Mg2 + 3-20%, Ca2 + 1-10%, Sr2 + 2-10%, Ba2 + 2-10%.
Ｒ１ ＋（Ｒ１ ＋はＬｉ＋、Ｎａ＋及びＫ＋の合計量）は、ガラスの溶融温度を下げるために有効な成分であるが、ガラスの化学的耐久性を低下させる成分でもある。近赤外線カットフィルタガラスに含まれる近赤外線カット成分の銅は、溶融温度が高いほど還元されやすい傾向にある。そして、ガラス成分中の２価の銅イオンＣｕ２＋が還元されると、紫外域に吸収をもつ１価の銅イオンＣｕ＋に変化し４００ｎｍ付近の可視域の透過率が低くなり、かつ近赤外域の透過率が高くなるという特性劣化の傾向が生じてしまう。
そのため、本発明においては、ガラスの溶融温度を下げるという点においては逆効果であるが、ガラスの化学的耐久性を高くするために、Ｒ１ ＋を１６．６％以下に抑える。Ｒ１ ＋の好ましい範囲は、３〜１３％である。なお、Ｐ５＋は、ガラス骨格を形成する成分で多量に含有すると耐候性の低下を招くとされていた。しかし本発明によれば、ガラスにＰ５＋を３５％以上含有したとしても、高い化学的耐久性が得られるものである。
R 1 + (R 1 + is the total amount of Li + , Na + and K + ) is an effective component for lowering the melting temperature of the glass, but is also a component that lowers the chemical durability of the glass. The near-infrared cut component copper contained in the near-infrared cut filter glass tends to be reduced as the melting temperature increases. When the divalent copper ion Cu 2+ in the glass component is reduced, it changes to a monovalent copper ion Cu + having absorption in the ultraviolet region, and the transmittance in the visible region near 400 nm is lowered, and near-red The tendency of characteristic deterioration that the transmittance of the outer region becomes high occurs.
Therefore, in the present invention, although it is counterproductive in terms of lowering the melting temperature of the glass, R 1 + is suppressed to 16.6 % or less in order to increase the chemical durability of the glass. The preferable range of R 1 + is 3 to 13%. Note that P 5+ is a component that forms a glass skeleton, and when contained in a large amount, P 5+ is said to cause a decrease in weather resistance. However, according to the present invention, even if the glass contains P 5+ in an amount of 35% or more, high chemical durability can be obtained.
Ｓｂ３＋は、ガラスの溶融温度を下げるために有効な成分であり、２％未満ではその効果がなく、１０％を超えると失透を生じやすくなるので好ましくない。Ｓｂ３＋の好ましい範囲は、４〜８％である。Ｓｂ３＋を上記のとおり含有することで、Ｒ１ ＋の含有量が少ないにも関わらず、ガラスの溶融温度を下げることができ、４００ｎｍ付近の可視域を効率よく透過することができる。 Sb 3+ is an effective component for lowering the melting temperature of the glass, and if it is less than 2%, it is not effective, and if it exceeds 10%, devitrification tends to occur, such being undesirable. A preferred range for Sb 3+ is 4-8%. By containing Sb 3+ as described above, the melting temperature of the glass can be lowered despite the small content of R 1 + , and the visible region near 400 nm can be efficiently transmitted.
Ｃｕ２＋は、近赤外線カットのための必須成分であり、０．５％未満では近赤外線カット効果が十分ではなく、１３％を超えるとガラスが不安定となる。好ましい範囲は、１〜１０％である。 Cu 2+ is an essential component for cutting near infrared rays. If it is less than 0.5%, the near infrared ray cutting effect is not sufficient, and if it exceeds 13%, the glass becomes unstable. A preferred range is 1 to 10%.
Ｆ−は、ガラスを安定化させ化学的耐久性を向上させるために有効であるが、１０％未満ではその効果が得られず、４５％を超えるとガラスの熱膨張係数が大きくなり、また成形時の粘性が低下するので好ましくない。Ｏ２−は、耐熱衝撃性を高め、Ｃｕ２＋イオンによるガラスの着色に寄与するが、５５％未満ではその効果が得られず、９０％を超えると溶融温度が高くなり、Ｃｕ２＋の還元をまねき所望の分光透過特性が得られなくなる。 F − is effective for stabilizing the glass and improving the chemical durability. However, if it is less than 10%, the effect cannot be obtained, and if it exceeds 45%, the thermal expansion coefficient of the glass is increased, and molding is also performed. This is not preferable because the viscosity at the time decreases. O 2− increases the thermal shock resistance and contributes to coloring of the glass with Cu 2+ ions. However, if it is less than 55%, the effect cannot be obtained, and if it exceeds 90%, the melting temperature becomes high, and Cu 2+ is reduced. The desired spectral transmission characteristics cannot be obtained.
本発明のガラスについて、ガラスを構成する成分（調合組成）を重量％で表すと、Ｐ２Ｏ５ ４０〜７０％、ＡｌＦ３ ０．２〜２０％、ＭｇＦ２＋ＣａＦ２＋ＳｒＦ２＋ＢａＦ２ １〜５０％、ＬｉＦ＋ＮａＦ＋ＫＦ ０〜１０％、Ｓｂ２Ｏ３ ４〜２０％、ただし、Ｆ ５〜３０％、Ｏ ２０〜５０％を含有する基礎ガラス１００重量部に対して、外割で、ＣｕＯ ０．５〜１６重量部を含むものである。これら各成分の好ましい範囲については、イオニック％表示にて説明した理由と同様である。
また、Ｐ２Ｏ５、ＡｌＦ３、ＭｇＦ２＋ＣａＦ２＋ＳｒＦ２＋ＢａＦ２、ＬｉＦ＋ＮａＦ＋ＫＦ、Ｓｂ２Ｏ３からなる基礎ガラスに対し、これら成分のほかに近赤外線カットフィルタガラスの特性を損なわない物質、たとえば、ＺｎＦ２、ＺｒＦ４、ＬａＦ３などを、ガラスの化学的耐久性、溶融性の改善や熱膨張係数の調整などを目的として１０％までの範囲で含有させることが可能である。
The glass of the present invention, expressed component constituting the glass (formulated composition) by weight%, P 2 O 5 40~70% , AlF 3 0.2~20%, MgF 2 + CaF 2 + SrF 2 + BaF 2 1~ 50%, LiF + NaF + KF 0 to 10%, Sb 2 O 3 4 to 20%, except for CuO 0. 10% by weight based on 100 parts by weight of the basic glass containing F 5 to 30% and
In addition to these components, a material that does not impair the properties of the near-infrared cut filter glass with respect to the basic glass composed of P 2 O 5 , AlF 3 , MgF 2 + CaF 2 + SrF 2 + BaF 2 , LiF + NaF + KF, Sb 2 O 3 , for example ZnF 2 , ZrF 4 , LaF 3 and the like can be incorporated in an amount of up to 10% for the purpose of improving the chemical durability and melting property of the glass and adjusting the thermal expansion coefficient.
ＤＳＣやカラービデオカメラに用いられる固体撮像素子用視感度補正フィルタは、湿った空気中において光学特性が変化しないことを確実にするため十分な化学的耐久性を持つことが望ましい。この化学的耐久性を評価するための代表的なテスト条件は、研磨後のガラスを温度６０℃、相対湿度９０％の条件下に保持し、ガラス研磨面に変質（腐食や再固化したガラス成分の沈着等）が目視検査にて確認されるまでの時間を測定するものである。 It is desirable that a visibility correction filter for a solid-state imaging device used in a DSC or a color video camera has sufficient chemical durability to ensure that optical characteristics do not change in humid air. A typical test condition for evaluating this chemical durability is that the polished glass is kept at a temperature of 60 ° C. and a relative humidity of 90%, and the glass polished surface is altered (corroded or re-solidified glass component). The time until the deposition is confirmed by visual inspection is measured.
本発明の近赤外線カットフィルタガラスは、上記テスト条件において、ガラス表面に変質が見られるまでの時間が１５００時間以上である。これにより、屋外に常設される監視用カラーカメラや車載カメラなど使用環境が苛酷な場合であっても、長期間ガラス表面に変質が生じることがない。よって、視感度補正フィルタの光学特性が変化することがないため、得られる画像も安定したものとなる。なお、上記テスト条件において、ガラス表面に変質が見られるまでの時間は、より好ましくは１８００時間以上である。 The near-infrared cut filter glass of the present invention has a time of 1500 hours or more until the glass surface is altered under the above test conditions. Thereby, even if the use environment such as a monitor color camera or an in-vehicle camera that is permanently installed outdoors is severe, the glass surface does not deteriorate for a long time. Therefore, since the optical characteristic of the visibility correction filter does not change, the obtained image becomes stable. In the above test conditions, the time until the alteration of the glass surface is observed is more preferably 1800 hours or longer.
本発明の近赤外線カットフィルタガラスは次のようにして作製することができる。まず得られるガラスが上記組成範囲になるように原料を秤量、混合する。この原料混合物を白金ルツボに収容し、蓋をして、電気炉内において７５０〜１０００℃の温度で加熱溶融する。十分に攪拌・清澄した後、金型内に鋳込み、徐冷した後、切断・研磨して内厚０．３ｍｍの平板状に成形する。なお、ルツボで溶融する場合は、白金製などの蓋でルツボを密閉してフッ素成分の揮発を抑えることで、ガラスの脈理を抑制することができる。本発明の近赤外線カットフィルタガラスは、溶融、成形工程を通じて、後の研磨工程で除去できないような目立った脈理の発生はなく、光学的にも均質なガラスを得ることができる。 The near-infrared cut filter glass of the present invention can be produced as follows. First, the raw materials are weighed and mixed so that the obtained glass has the above composition range. This raw material mixture is accommodated in a platinum crucible, covered, and heated and melted at a temperature of 750 to 1000 ° C. in an electric furnace. After sufficiently stirring and clarifying, it is cast into a mold, slowly cooled, then cut and polished to form a flat plate having an inner thickness of 0.3 mm. In the case of melting with a crucible, glass striae can be suppressed by sealing the crucible with a lid made of platinum or the like to suppress volatilization of the fluorine component. The near-infrared cut filter glass of the present invention does not generate striking striae that cannot be removed in the subsequent polishing process through the melting and molding processes, and an optically homogeneous glass can be obtained.
本発明の固体撮像素子用視感度補正フィルタは、上記のようにして作成した近赤外線カットフィルタガラスを切断、研削、研磨、面取などの機械加工を施して、最終的に両面が光学研磨された薄板状に成形したものである。この視感度補正フィルタは、上記ガラスからなり、近赤外線に吸収特性を有するので、これにより撮像素子に対する視感度補正を行うことができる。使用されるフィルタの厚さは、組み合わされる撮像素子側の要求特性に応じて、近赤外線吸収物質であるＣｕＯ含有量などのガラス組成と合せて適切な透過特性が得られるように調整して使用される。一般的なＤＳＣなどでは、０．１〜１ｍｍ程度、好ましくは０．２〜０．５ｍｍ程度の厚さで用いられる。フィルタの使用態様としては、本発明の視感度補正フィルタを２枚の水晶板で挟んで接着したものや片面のみに水晶板を接着したもの、あるいは光学ガラスに貼り合わせるなどして使用することができる。また、フィルタの表面には必要に応じて反射防止膜、紫外線・赤外線カット膜などの光学多層膜を真空蒸着など周知の手段によって形成することができる。 The visibility correction filter for a solid-state imaging device of the present invention is subjected to mechanical processing such as cutting, grinding, polishing, and chamfering of the near-infrared cut filter glass prepared as described above, and finally both surfaces are optically polished. It is formed into a thin plate shape. This visibility correction filter is made of the above glass and has an absorption characteristic in the near infrared, so that the visibility correction for the image sensor can be performed. The thickness of the filter to be used is adjusted according to the required characteristics on the image sensor side to be combined and adjusted so that appropriate transmission characteristics can be obtained in combination with the glass composition such as the CuO content that is a near-infrared absorbing material. Is done. In a general DSC, the thickness is about 0.1 to 1 mm, preferably about 0.2 to 0.5 mm. As a usage mode of the filter, the visibility correction filter of the present invention is sandwiched between two quartz plates, bonded to only one side, or bonded to optical glass. it can. Further, an optical multilayer film such as an antireflection film or an ultraviolet / infrared cut film can be formed on the surface of the filter as required by a known means such as vacuum deposition.
本発明のフィルタは、主として固体撮像素子の視感度補正に用いられることから、撮像装置の撮影レンズと撮像素子との間の光路上に配設されて使用され、上記近赤外線の吸収特性により良好な視感度補正を行うことができる。また、本発明のガラスは非常に優れた化学的耐久性を有しているので、ガラスにウエザリングが発生しにくく長期間にわたって良好な光学特性を維持できる。 Since the filter of the present invention is mainly used for correcting the visibility of a solid-state imaging device, it is used by being disposed on the optical path between the imaging lens of the imaging device and the imaging device, and is better due to the absorption characteristics of the near infrared rays. Visual sensitivity correction can be performed. Further, since the glass of the present invention has very excellent chemical durability, weathering is hardly generated in the glass, and good optical characteristics can be maintained over a long period of time.
本発明の実施例を表１に示す。表１中のガラス組成はイオニック％で示す。また、化学的耐久性（耐候性）は研磨したガラスを温度６０℃、相対湿度９０％の条件下に保持し、ガラス表面に変質が見られるまでの時間を示したものである。また、実施例Ｎｏ．２及び比較例Ｎｏ．８について、日本分光株式会社製のＵＶ−ＩＲ分光光度計Ｖ−５７０を用い、ガラス表面に反射防止膜などを被着していないガラス単体での分光透過率曲線を測定した。なお表１中、Ｎｏ．１、Ｎｏ．３〜６は本発明による実施例、Ｎｏ．７〜１０は比較例、Ｎｏ．２は参考例である。 Examples of the present invention are shown in Table 1. The glass composition in Table 1 is expressed in ionic%. The chemical durability (weather resistance) indicates the time until the glass surface is altered by holding the polished glass at a temperature of 60 ° C. and a relative humidity of 90%. In addition, Example No. 2 and Comparative Example No. 8 was measured using a UV-IR spectrophotometer V-570 manufactured by JASCO Corporation, and the spectral transmittance curve of a single glass having no antireflection film or the like applied to the glass surface was measured. In Table 1, No. 1 , no. 3 to 6 are examples according to the present invention, No. 7 to 10 are comparative examples . 2 is a reference example .
実施例の各ガラスは、耐候性が１５００時間以上であり、比較例の各ガラスと比べ化学的耐久性が高いことが確認された。また、図１に実施例Ｎｏ．２と比較例Ｎｏ．８のガラスの分光透過率曲線を示す。これらのガラスは、Ｃｕ２＋の含有量が同一であるが、Ｒ１ ＋（Ｌｉ＋、Ｎａ＋及びＫ＋の合計量）及びＳｂ３＋の含有量が大きく異なる。実施例Ｎｏ．２のガラスは、Ｓｂ３＋の含有量が多いため、ガラスの溶融温度を下げることができ、これにより比較例Ｎｏ．８のガラスに比べ実施例Ｎｏ．２のガラスの方が４００ｎｍ付近の可視域の透過率が高いことがわかる。 Each glass of the examples had a weather resistance of 1500 hours or more, and it was confirmed that the chemical durability was higher than each glass of the comparative example. In addition, FIG. 2 and Comparative Example No. 8 shows the spectral transmittance curve of No. 8 glass. Although these glasses have the same Cu 2+ content, the contents of R 1 + (total amount of Li + , Na + and K + ) and Sb 3+ differ greatly. Example No. Since the glass of No. 2 has a large content of Sb 3+ , the melting temperature of the glass can be lowered. Compared to the glass of No. 8, Example No. It can be seen that the glass No. 2 has a higher transmittance in the visible region near 400 nm.
以上のように本発明の近赤外線カットフィルタガラスは、化学的耐久性が非常に優れているので、屋外で使用される監視用カメラ等の視感度補正フィルタとして極めて有用なものである。 As described above, the near-infrared cut filter glass of the present invention is very useful as a visibility correction filter for surveillance cameras and the like used outdoors because it has excellent chemical durability.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008219908A JP5251365B2 (en) | 2008-08-28 | 2008-08-28 | Near-infrared cut filter glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008219908A JP5251365B2 (en) | 2008-08-28 | 2008-08-28 | Near-infrared cut filter glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010052987A JP2010052987A (en) | 2010-03-11 |
| JP5251365B2 true JP5251365B2 (en) | 2013-07-31 |
Family
ID=42069298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008219908A Active JP5251365B2 (en) | 2008-08-28 | 2008-08-28 | Near-infrared cut filter glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5251365B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI555717B (en) * | 2010-12-23 | 2016-11-01 | 史考特公司 | Fluorophosphate glasses |
| JP5721781B2 (en) * | 2012-06-29 | 2015-05-20 | 株式会社オハラ | Optical glass, optical element and preform |
| CN106164002A (en) * | 2014-04-09 | 2016-11-23 | 旭硝子株式会社 | Near infrared cut-off filters glass |
| CN109748497B (en) * | 2017-11-02 | 2023-09-08 | Hoya株式会社 | Optical glass and optical element |
| CN114538772B (en) * | 2022-03-24 | 2022-12-02 | 成都光明光电股份有限公司 | Glass, glass element and optical filter |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11209144A (en) * | 1998-01-21 | 1999-08-03 | Hoya Corp | Glass for near infrared ray absorbing filter and near infrared ray absorbing filter using the same |
| JP4169545B2 (en) * | 2002-07-05 | 2008-10-22 | Ｈｏｙａ株式会社 | Near-infrared light absorbing glass, near-infrared light absorbing element, near-infrared light absorbing filter, and method for producing near-infrared light absorbing glass molded body |
| JP3965352B2 (en) * | 2002-10-16 | 2007-08-29 | Ｈｏｙａ株式会社 | Copper-containing glass, near infrared light absorption element, and near infrared light absorption filter |
| JP2007099604A (en) * | 2005-09-06 | 2007-04-19 | Hoya Corp | Near infrared ray absorbing glass, near infrared ray absorbing element provided with the same and imaging device |
| JP4953347B2 (en) * | 2006-06-21 | 2012-06-13 | Ａｇｃテクノグラス株式会社 | Visibility correction filter glass and visibility correction filter |
-
2008
- 2008-08-28 JP JP2008219908A patent/JP5251365B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010052987A (en) | 2010-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6332916B2 (en) | Colored glass | |
| US20070099787A1 (en) | Aluminophosphate glass containing copper (II) oxide and uses thereof for light filtering | |
| JP3965352B2 (en) | Copper-containing glass, near infrared light absorption element, and near infrared light absorption filter | |
| JP2011132077A (en) | Near-infrared light absorbing glass, near-infrared light absorbing filter, and imaging device | |
| TWI725213B (en) | Optical glass and near infrared cut filter | |
| JP5672300B2 (en) | Manufacturing method of near infrared cut filter glass | |
| JP5036229B2 (en) | Visibility correction filter glass and visibility correction filter | |
| JP5051817B2 (en) | Visibility correction filter glass and visibility correction filter | |
| JP5251365B2 (en) | Near-infrared cut filter glass | |
| JP5057505B2 (en) | Visibility correction filter glass manufacturing method | |
| JP4953347B2 (en) | Visibility correction filter glass and visibility correction filter | |
| JP4925243B2 (en) | Near-infrared cut filter glass | |
| JP2006248850A (en) | Glass for near-infrared absorbing filter | |
| CN107406304B (en) | Near infrared ray cut-off filter glass | |
| WO2014103675A1 (en) | Glass | |
| JP6992494B2 (en) | Near infrared cut filter glass and near infrared cut filter | |
| JPH0616451A (en) | Filter glass for cutting near-infrared rays | |
| JP2006182584A (en) | Filter glass for cutting near-infrared ray | |
| JP3396387B2 (en) | Near infrared cut filter glass | |
| JP2006182586A (en) | Filter glass for cutting near-infrared ray | |
| JP6962322B2 (en) | Near infrared cut filter glass | |
| TWI522331B (en) | Near infrared light absorption glass, components and filters | |
| JP2006182585A (en) | Filter glass for cutting near-infrared ray | |
| JP2003160358A (en) | Filter glass for cutting near-infrared ray | |
| TWI542562B (en) | Optical glass, preform and optical element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110308 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121015 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121113 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130111 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130319 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130401 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5251365 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160426 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |