JPH0692259B2 - Near infrared cut filter glass - Google Patents
Near infrared cut filter glassInfo
- Publication number
- JPH0692259B2 JPH0692259B2 JP17304191A JP17304191A JPH0692259B2 JP H0692259 B2 JPH0692259 B2 JP H0692259B2 JP 17304191 A JP17304191 A JP 17304191A JP 17304191 A JP17304191 A JP 17304191A JP H0692259 B2 JPH0692259 B2 JP H0692259B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- infrared cut
- near infrared
- cut filter
- filter glass
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カラーＶＴＲカメラの
色補正フィルタ等に使用され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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared cut filter glass which is used as a color correction filter for a color VTR camera and which efficiently transmits a visible region of 400 to 600 nm and has an excellent sharp cut characteristic near 700 nm.
【０００２】[0002]
【従来の技術】カラーＶＴＲカメラに使用されている撮
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。したがって、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、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。2. Description of the Related Art An image pickup device used in a color VTR camera has a spectral sensitivity ranging from a visible region to a near infrared region around 1100 nm. Therefore, since good color reproducibility cannot be obtained as it is, it is necessary to correct to normal luminosity by using a filter that absorbs the infrared region.
【０００３】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Ｐ2 Ｏ
5 と必須成分としてＣｕＯを含有しており、酸化性の溶
融雰囲気中で、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 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
Containing 5 and CuO as an essential component, which exhibits a blue-green color by forming Cu 2+ ions coordinated with a large number of oxygen ions in an oxidizing molten atmosphere, and has near-infrared cut characteristics Is.
【０００４】また、最近ではリン酸塩系ガラスの耐候性
の低さを改善するために基礎ガラスとして弗燐酸塩系ガ
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
弗燐酸塩系ガラスなどが開発されている。Recently, in order to improve the low weather resistance of phosphate glass, fluorophosphate glass is used as the basic glass and CuO is added to the glass, for example, Japanese Patent Laid-Open No. 1-219037. The fluorophosphate glass described in JP-A-3-83834 has been developed.
【０００５】[0005]
【発明が解決しようとする課題】しかし、前記の燐酸塩
系ガラスは、近赤外線カット効果を促進するためにＣｕ
Ｏ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の波長域におけるシャー
プカット特性が悪化するという問題点がある。特にこの
ようなフィルタガラスは、薄板状で使用されることから
高いＣｕＯ含有量を要求されるが、前記問題点により所
望の分光透過性を有するものが得難い。また基礎ガラス
である燐酸塩系ガラスは、耐候性が不十分なため、ガラ
ス研磨面にウェ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。However, the above-mentioned phosphate-based glass contains Cu in order to promote the near infrared ray cutting effect.
Increasing the O content generally results in 400-500 nm
There is a problem in that the spectral transmittance in the wavelength range of 1) decreases, the greening tendency tends to occur, and the sharp cut characteristic in the wavelength range of 600 to 700 nm deteriorates. In particular, such a filter glass is required to have a high CuO content because it is used in the form of a thin plate, but it is difficult to obtain a filter glass having a desired spectral transmittance due to the above problems. Further, since the phosphate glass, which is the basic glass, has insufficient weather resistance, it causes weathering on the polished surface of the glass, so that it is difficult to use it for a long period of time.
【０００６】また、上記弗燐酸塩系ガラスは、失透しや
すいうえガラスの耐候性確保のためＰ2 Ｏ5 含有量を低
く抑えると、熱膨張係数が大きくなり熱衝撃に弱いとい
う欠点がある。溶融後固化したガラスをフィルタとして
用いるには、研削、研磨等の工程を経るが、上記弗燐酸
塩系ガラスは、５０〜１００℃の温度差でヒートショッ
クによるクラックを生じるため成形加工工程での歩留が
極めて低い。Further, the fluorophosphate glass is liable to devitrify, and if the P 2 O 5 content is kept low to secure the weather resistance of the glass, the coefficient of thermal expansion becomes large and it is weak against thermal shock. . In order to use the glass solidified after melting as a filter, steps such as grinding and polishing are performed, but the fluorophosphate glass causes cracks due to heat shock at a temperature difference of 50 to 100 ° C. The yield is extremely low.
【０００７】本発明は、このような事情を考慮してなさ
れたもので、所望の分光透過特性を保持しながら化学的
耐久性に優れ、かつ耐熱衝撃性の高い近赤外線カットフ
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 consideration of such circumstances, and provides a near infrared cut filter glass having excellent chemical durability while maintaining desired spectral transmission characteristics and high thermal shock resistance. The purpose is to
【０００８】[0008]
【課題を解決するための手段】本発明は上記目的を達成
するために、燐酸塩系ガラスにＦを導入して化学的耐久
性を向上させるとともにＰ2 Ｏ5 含有量を下記の範囲内
に制御することにより失透を防止し、成形加工性を向上
させたものである。すなわち本発明は、重量％で、Ｐ2
Ｏ5 ４６〜７０％，ＡｌＦ3 ０．２〜２０％，Ｍｇ
Ｆ2 ＋ ＣａＦ 2 ＋ＳｒＦ2 ＋ＢａＦ2 ＋ＰｂＦ2 １
〜５０％，ＬｉＦ＋ＮａＦ＋ＫＦ ０〜２５％，ただ
し、Ｆ ０．５〜３２％，Ｏ ２６〜５４％を含有する
基礎ガラス１００重量部に対しＣｕＯ ０．５〜７重量
部を含むことを特徴とする近赤外線カットフィルタガラ
スである。The present invention achieves the above object.
In order to improve the chemical durability
And improve P2OFiveContent within the following range
To prevent devitrification and improve moldability
It was made. That is, the present invention is based on P% by weight.2
OFive 46-70%, AlF3 0.2-20%, Mg
F2+ CaF 2+ SrF2+ BaF2+ PbF2 1
~ 50%, LiF + NaF + KF 0-25%, just
And contains 0.5 to 32% of F and 26 to 54% of O.
CuO 0.5 to 7 parts by weight with respect to 100 parts by weight of basic glass
Infrared cut filter glass characterized by including parts
It is.
【０００９】[0009]
【作用】以下に本発明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。The action of each component constituting the present invention and the reason for limiting the composition range as described above will be described below.
【００１０】Ｐ2 Ｏ5 はガラスの網目構造を形成する主
成分であるが、４６％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。７０％を越えると化学的耐久性が低下する。ＡｌＦ
3 は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、２
０％を越えるとガラス化が困難となる。ＭｇＦ2 ，Ｃａ
Ｆ2 ，ＳｒＦ2 ，ＢａＦ2 ，ＰｂＦ2 は化学的耐久性を
低下することなくガラスを安定化するのに効果がある
が、上記範囲をはずれるとガラスが不安定となり、失透
を生じやすくするので好ましくない。ＬｉＦ，ＮａＦ，
ＫＦは溶融温度を下げるために有効な成分であるが、こ
れらの合量が２５％を越えると化学的耐久性を著しく低
下させる。P 2 O 5 is a main component for forming a network structure of glass, but if it is less than 46%, the stability of the glass is deteriorated, and the coefficient of thermal expansion is increased and the thermal shock resistance is lowered. If it exceeds 70%, the chemical durability is lowered. AlF
3 is a component that improves the chemical durability and increases the viscosity of glass, but if it is less than 0.2%, its effect cannot be obtained.
If it exceeds 0%, vitrification becomes difficult. MgF 2 , Ca
F 2 , SrF 2 , BaF 2 , and PbF 2 are effective in stabilizing the glass without lowering the chemical durability, but if it is out of the above range, the glass becomes unstable and devitrification easily occurs. It is not preferable. LiF, NaF,
KF is an effective component for lowering the melting temperature, but if the total amount of these exceeds 25%, the chemical durability will be significantly reduced.
【００１１】また、上記弗化物を酸化物に置換して添加
することが可能である。この場合、ＦおよびＯの量はそ
れぞれ上記範囲内であることが好ましい。すなわち、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、０．５％未満ではその効果が得られず、
３２％を越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。Ｏ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、２６％未満ではその効果が得られず、５４％を
越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。Further, it is possible to add the above-mentioned fluoride by substituting it with an oxide. In this case, the amounts of F and O are preferably within the above ranges. That is, F
Is effective for stabilizing glass and improving chemical durability, but if it is less than 0.5%, the effect cannot be obtained,
If it exceeds 32%, the coefficient of thermal expansion of glass becomes large and the viscosity at the time of molding decreases, which is not preferable. O enhances the thermal shock resistance and contributes to the coloring of the glass by Cu 2+ ions, but if it is less than 26%, the effect cannot be obtained, and if it exceeds 54%, the melting temperature becomes high, leading to the reduction of Cu 2+. The desired spectral transmission characteristics cannot be obtained.
【００１２】ＣｕＯは近赤外線カットのための必須成分
であるが、０．５％未満ではその効果がなく、７％を越
えると可視域における透過率を低下させるので好ましく
ない。CuO is an essential component for cutting near-infrared rays, but if it is less than 0.5%, it has no effect, and if it exceeds 7%, it lowers the transmittance in the visible region, which is not preferable.
【００１３】[0013]
【実施例】本発明の実施例を表１に示す。表１中のガラ
ス組成は重量％で示し、耐候性（化学的耐久性）は研磨
したガラスを温度６０℃、相対湿度９５％の条件下に保
持し、ガラスの表面に変質が見られるまでの時間を示し
たものである。なお表１中、１〜１０は本発明による実
施例、１１，１２は燐酸塩系ガラスを基礎ガラスとする
比較例、１３，１４は弗燐酸塩系ガラスを基礎ガラスと
する比較例である。EXAMPLES Examples of the present invention are shown in Table 1. The glass composition in Table 1 is shown by weight%, and the weather resistance (chemical durability) is such that the polished glass is kept under the conditions of a temperature of 60 ° C. and a relative humidity of 95% until the glass surface is altered. It shows the time. In Table 1, 1 to 10 are examples according to the present invention, 11 and 12 are comparative examples using a phosphate glass as a basic glass, and 13 and 14 are comparative examples using a fluorophosphate glass as a basic glass.
【００１４】表１に示したガラスは、いずれも所定の組
成となるように原料を混合し、白金ルツボに収容して蓋
をして８００〜１１００℃の温度で溶融し、攪拌・清澄
後金型内に鋳込み、徐冷した後、切断・研磨して肉厚２
ｍｍの平板状に成形した。The glasses shown in Table 1 are prepared by mixing the raw materials so that each of them has a predetermined composition, accommodating them in a platinum crucible, covering them with a lid, melting at a temperature of 800 to 1100 ° C., stirring and refining the gold. It is cast in a mold, slowly cooled, then cut and polished to a wall thickness of 2
It was formed into a flat plate of mm.
【００１５】[0015]
【表１】 [Table 1]
【００１６】以上のようにして作製した平板状のガラス
について分光透過率を測定した。実施例Ｎo.６と比較例
Ｎo.１１のガラスについての測定結果を図１に示す。図
１から明らかなように、本発明に係る実施例のガラス
は、比較例のガラスに較べて４００〜５００ｎｍでの透
過率が高く、６００〜７００ｎｍにかけてのシャープカ
ット性に優れている。また耐候性試験の結果、比較例の
燐酸塩系ガラスでは２４０時間前後で表面に変質が見ら
れたのに対し、本実施例および比較例Ｎo.１３，１４の
ガラスでは８００時間以上表面変質は認められなかっ
た。しかしながら比較例Ｎo.１３，１４のガラスは、熱
膨張係数が１４０×１０-7／℃以上あり、研磨加工時に
破損するものが頻出した。これに対し本実施例のガラス
は、熱膨張係数が大きくても１１５×１０-7／℃程度で
あり、加工工程全般にわたる破損率が低く、加工歩留ま
りの点でも優れている。The spectral transmittance of the flat glass produced as described above was measured. The measurement results of the glasses of Example No. 6 and Comparative Example No. 11 are shown in FIG. As is apparent from FIG. 1, the glass of the example according to the present invention has a higher transmittance at 400 to 500 nm than the glass of the comparative example and is excellent in sharp cut property from 600 to 700 nm. In addition, as a result of the weather resistance test, the phosphate glass of the comparative example showed surface alteration around 240 hours, whereas the glass of the present example and comparative examples No. 13 and 14 showed surface alteration of 800 hours or more. I was not able to admit. However, the glass of Comparative Examples Nos. 13 and 14 had a coefficient of thermal expansion of 140 × 10 −7 / ° C. or more, and many of them were broken during polishing. On the other hand, the glass of this example has a thermal expansion coefficient of about 115 × 10 −7 / ° C. even if it is large, the damage rate is low throughout the processing steps, and the processing yield is also excellent.
【００１７】[0017]
【発明の効果】以上のように本発明のガラスフィルタ
は、従来用いられていた燐酸塩系ガラスフィルタに較べ
て極めて優れた化学的耐久性を持ち、可視域におけるシ
ャープカット性に優れた初期分光透過特性を長期間にわ
たって維持することができるので、カラーＶＴＲカメラ
の色補正フィルタや他の感光素子の視感度補正フィルタ
として極めて有用なものである。。また本発明のガラス
は、従来の弗燐酸塩系ガラスの欠点であった失透化傾向
が低く改善され、耐熱衝撃性にも優れるので、成形・加
工歩留が向上するという効果がある。INDUSTRIAL APPLICABILITY As described above, the glass filter of the present invention has extremely excellent chemical durability as compared with the conventionally used phosphate-based glass filters, and has an excellent initial sharp spectrum in the visible region. Since the transmission characteristics can be maintained for a long period of time, it is extremely useful as a color correction filter for a color VTR camera and a visibility correction filter for other photosensitive elements. . Further, the glass of the present invention has a low devitrification tendency which is a drawback of the conventional fluorophosphate type glass and is improved, and is also excellent in thermal shock resistance, so that there is an effect that the molding / processing yield is improved.
【図１】本発明に係る実施例ガラスおよび比較例ガラス
の分光透過特性を示す曲線図である。FIG. 1 is a curve diagram showing spectral transmission characteristics of an example glass and a comparative example glass according to the present invention.
１ 実施例ガラス（Ｎo.６） ２ 比較例ガラス（Ｎo.11） 1 Example glass (No. 6) 2 Comparative example glass (No. 11)
Claims (1)
ｌＦ3 ０．２〜２０％，ＭｇＦ2 ＋ＣａＦ2 ＋ＳｒＦ
2 ＋ＢａＦ2 ＋ＰｂＦ2 １〜５０％，ＬｉＦ＋ＮａＦ
＋ＫＦ ０〜２５％，ただし、Ｆ ０．５〜３２％，Ｏ
２６〜５４％を含有する基礎ガラス１００重量部に対
しＣｕＯ ０．５〜７重量部を含むことを特徴とする近
赤外線カットフィルタガラス。1. P 2 O 5 46-70% by weight, A
lF 3 0.2~20%, MgF 2 + CaF 2 + SrF
2 + BaF 2 + PbF 2 1~50 %, LiF + NaF
+ KF 0-25%, but F 0.5-32%, O
A near-infrared cut filter glass containing 0.5 to 7 parts by weight of CuO with respect to 100 parts by weight of base glass containing 26 to 54%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17304191A JPH0692259B2 (en) | 1991-06-18 | 1991-06-18 | Near infrared cut filter glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17304191A JPH0692259B2 (en) | 1991-06-18 | 1991-06-18 | Near infrared cut filter glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0616451A JPH0616451A (en) | 1994-01-25 |
| JPH0692259B2 true JPH0692259B2 (en) | 1994-11-16 |
Family
ID=15953111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17304191A Expired - Lifetime JPH0692259B2 (en) | 1991-06-18 | 1991-06-18 | Near infrared cut filter glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692259B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1466875A3 (en) * | 2003-04-09 | 2007-05-30 | Hoya Corporation | Glass for window of semiconductor package, glass window for semiconductor package, process for production of glass window, and semiconductor package |
| JP2006182585A (en) * | 2004-12-27 | 2006-07-13 | Asahi Techno Glass Corp | Filter glass for cutting near-infrared ray |
| JP4925243B2 (en) * | 2005-06-09 | 2012-04-25 | Ａｇｃテクノグラス株式会社 | Near-infrared cut filter glass |
| JP4546379B2 (en) * | 2005-09-30 | 2010-09-15 | 日本山村硝子株式会社 | Near infrared filter glass |
| JP2008044813A (en) * | 2006-08-15 | 2008-02-28 | Fujinon Corp | Optical glass |
| WO2010119964A1 (en) * | 2009-04-17 | 2010-10-21 | 旭硝子株式会社 | Filter glass cutting near infrared rays |
| JP5801773B2 (en) | 2011-08-11 | 2015-10-28 | Hoya株式会社 | Fluorophosphate glass, method for producing the same, and near infrared light absorption filter |
| JP6642575B2 (en) | 2015-07-31 | 2020-02-05 | Ａｇｃ株式会社 | Optical filter and near infrared cut filter |
| JP2019038732A (en) * | 2017-08-29 | 2019-03-14 | 日本電気硝子株式会社 | Near-infrared radiation absorption glass |
| WO2019044563A1 (en) * | 2017-08-31 | 2019-03-07 | Ａｇｃ株式会社 | Glass |
-
1991
- 1991-06-18 JP JP17304191A patent/JPH0692259B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0616451A (en) | 1994-01-25 |
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