JP2515672B2 - Optical glass showing positive anomalous partial dispersion in the blue region - Google Patents
Optical glass showing positive anomalous partial dispersion in the blue regionInfo
- Publication number
- JP2515672B2 JP2515672B2 JP4240070A JP24007092A JP2515672B2 JP 2515672 B2 JP2515672 B2 JP 2515672B2 JP 4240070 A JP4240070 A JP 4240070A JP 24007092 A JP24007092 A JP 24007092A JP 2515672 B2 JP2515672 B2 JP 2515672B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- bao
- content
- partial dispersion
- 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.)
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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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、青色領域で正の異常部
分分散を示し、１．４９〜１．５４の屈折率ｎd 及び７
１〜８４のアッベ数νd を有する光学ガラスに関する。BACKGROUND OF THE INVENTION The present invention exhibits a positive anomalous partial dispersion in the blue region and has a refractive index n d of 7 and a refractive index n d of 1.49 to 1.54.
It relates to an optical glass having an Abbe number ν d of 1 to 84.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】異常部分
分散を示すガラスは、いわゆる二次スペクトルの補正に
利用される。その際、好ましくは標準直線からの偏差が
特に大きいガラスが使用される。光学ガラスの屈折率と
波長との依存関係を特徴付けるため、屈折率ｎd は一般
に波長を５８７．５６ｎｍ、アッベ数をνd として下記
化１の式で表わされる。BACKGROUND OF THE INVENTION Glasses exhibiting anomalous partial dispersion are used for so-called secondary spectrum correction. In that case, glass having a particularly large deviation from the standard line is preferably used. In order to characterize the dependency between the refractive index of optical glass and the wavelength, the refractive index n d is generally expressed by the following formula 1 where the wavelength is 587.56 nm and the Abbe number is ν d .
【０００３】[0003]
【化１】 ここで、ｎF は波長４８６．１３ｎｍでの屈折率、ｎc
は波長６５６．２７ｎｍでの屈折率を意味する。Embedded image Here, n F is the refractive index at a wavelength of 486.13 nm, and n c
Means the refractive index at a wavelength of 656.27 nm.
【０００４】スペクトルの青色領域での部分分散能は、
下記化２の式で表わされる。The partial dispersion power in the blue region of the spectrum is
It is expressed by the following formula 2.
【化２】 ここで、ｎg は波長４３５．８３ｎｍでの屈折率を意味
する。Embedded image Here, ng means a refractive index at a wavelength of 435.83 nm.
【０００５】数多くのガラス、いわゆる標準ガラスは、
下記化３の線形関係を近似的に満足する。Many glasses, so-called standard glasses,
The linear relation of the following chemical formula 3 is approximately satisfied.
【化３】Ｐ’X, Y＝ＡX, Y＋ＢX, Y・νd [Chemical 3] P'X , Y = A X, Y + B X, Y · ν d
【０００６】ガラスＫ７及びＦ２（１９８０年独マイン
ツのショット・グラスヴェルケ社（Ｓｃｈｏｔｔ Ｇｌ
ａｓｗｅｒｋｅ）発行のショット−カタログ「光学ガラ
ス」参照）については、部分分散能を示す直線、即ち標
準直線は、スペクトルの青色領域では下記化４の式で示
される。Glasses K7 and F2 (Schott Glke, Mainz Germany, 1980)
As for the shot published by Aswerke-see catalog "Optical glass"), the straight line showing the partial dispersion power, that is, the standard straight line is represented by the following formula 4 in the blue region of the spectrum.
【化４】 Ｐ’g,F ＝０．６４３８−０．００１６８２・νd この曲線からの偏りを有するガラスは、異常部分分散を
有する。偏差の尺度としては縦座標差△Ｐg,F が用いら
れ、この差分だけ当該値が標準直線に対しずれている。
この値が＞０であると、ガラスは正方向に偏差した部分
分散を有するガラスと呼ばれる。## STR00004 ## P'g , F = 0.6438-0.001682.v d Glass with a deviation from this curve has anomalous partial dispersion. The ordinate difference ΔP g, F is used as a measure of the deviation, and the value is deviated from the standard line by this difference.
If this value is> 0, the glass is said to have a positively deviated partial dispersion.
【０００７】ドイツ特許公開明細書第３０ ４４ ２４
１号には正の異常部分分散を有するフツリン酸塩ガラス
が記載されているが、しかしこのガラスはフッ化カルシ
ウム含量が高いので化学的耐久性が比較的低い。ドイツ
特許明細書第１４ ９６ ５６６号にはＡｌ2 Ｏ3 含量
が比較的低いガラスが記載されているが、しかもなおＫ
2 Ｏを最低量含有していなければならない。これにより
ガラスの溶融温度が低下するのではあるが、しかし相分
離傾向も高まる。German Patent Publication No. 30 44 24
No. 1 describes a fluorophosphate glass with a positive anomalous partial dispersion, but this glass has a relatively low chemical durability due to its high calcium fluoride content. German Patent Specification No. 14 96 566 describes glasses with a relatively low Al 2 O 3 content, but still K
Must contain a minimum amount of 2 O. This lowers the melting temperature of the glass, but also increases the tendency for phase separation.
【０００８】ドイツ特許明細書第９４５ ４０８号には
存在領域のきわめて広いガラスが記載されているが、正
の異常部分分散については何ら言及されていない。この
ガラスは部分的に、その使用が今日では労働衛生上の理
由から拒絶される諸成分を含み、また部分的には、例え
ば知られているように短波長域で強い吸収を引き起こ
す、酸化鉛等の意図した利用目的にとって否定的な光学
特性を有する諸成分も含有している。従って、ドイツ特
許明細書第９４５ ４０８号に記載の溶融可能な多数の
ガラスは、正の異常部分分散性でないと考えねばならな
い。German patent specification 945 408 describes glasses with a very wide range of existence, but does not mention any positive anomalous partial dispersion. This glass partly contains lead oxides whose use is today rejected for industrial hygiene reasons and also partly causes strong absorption in the short wavelength range, as is known, for example. It also contains various components having optical characteristics that are negative for the intended purpose of use. Therefore, the large number of meltable glasses described in German patent specification 945 408 must be considered not to have a positive anomalous partial dispersion.
【０００９】ドイツ特許明細書第３１ ２３ ０５７号
に記載のガラスはフッ素含量が高く、これにより、記載
されたガラスの失透傾向が著しく高まる。ドイツ特許明
細書第３０ ４３ ６１５号に記載されたガラスはＰ2
Ｏ5 含量が比較的低く、またＡｌ2 Ｏ3 含量が比較的高
い。一方では、Ａｌ2 Ｏ3 含量によりガラスの易結晶化
性が高まり、他方では、これらのガラスはＰ2 Ｏ5 低含
量の故に網状結合成分が少なく、従って失透傾向が高
い。ドイツ特許公告明細書第１７ ７１ ６９２号に記
載のガラスは、ごく微量のＡｌ2 Ｏ3 を含有し、ＢａＴ
ｉＦ6 又はＫ2 ＴｉＦ6 等の錯成分も常に含有してい
る。しかし、チタン化合物分が紫外帯域の故に紫外透過
率に否定的に作用する。しかもＴｉＯ2 の添加が溶融温
度を著しく高め、これによりるつぼ材料への侵食作用が
高まる。The glass described in German patent specification 31 23 057 has a high fluorine content, which significantly increases the devitrification tendency of the glass described. The glass described in German patent specification 30 43 615 is P 2
The O 5 content is relatively low and the Al 2 O 3 content is relatively high. On the one hand, the Al 2 O 3 content increases the crystallinity of the glass, and on the other hand, these glasses are low in reticulated components due to their low P 2 O 5 content and therefore have a high devitrification tendency. The glass described in German Patent Publication No. 17 71 692 contains a very small amount of Al 2 O 3 and is
It also always contains complex components such as iF 6 or K 2 TiF 6 . However, the titanium compound component negatively affects the ultraviolet transmittance due to the ultraviolet band. Moreover, the addition of TiO 2 significantly raises the melting temperature, which enhances the erosive action on the crucible material.
【００１０】本発明の目的は、屈折率ｎd を１．４９〜
１．５４の間で、アッベ数νd を７１〜８４の間で変更
することができ、少なくとも＋０．０２の、部分分散の
標準直線からの正方向偏差△Ｐg,F が得られる光学ガラ
スを見い出すことにある。このガラスは更に失透に対し
高い抵抗性と良好な再現性と良好な透過能を有していな
ければならない。An object of the present invention is to have a refractive index n d of 1.49 to
An optical glass in which the Abbe number ν d can be changed between 71 and 84 between 1.54 and a positive deviation ΔP g, F from the standard line of partial dispersion of at least +0.02 is obtained. To find out. The glass must also have high resistance to devitrification, good reproducibility and good transmission.
【００１１】[0011]
【課題を解決するための手段】前記目的を達成するた
め、本発明によれば、以下の組成 ＳｉＯ2 ０ 〜 ２ 重量％ ＧｅＯ2 ０ 〜 ２ 重量％ ΣＳｉＯ2 ＋ＧｅＯ2 ０ 〜 ２ 重量％ Ｂ2 Ｏ3 ０ 〜 ２ 重量％ Ａｌ2 Ｏ3 ６ 〜１３．５重量％ Ｌｉ2 Ｏ ０ 〜 ３ 重量％ Ｎａ2 Ｏ ０ 〜 ３ 重量％ Ｋ2 Ｏ ０ 〜 ３ 重量％ Σアルカリ酸化物 ０ 〜 ３ 重量％ ＭｇＯ ０ 〜１０ 重量％ ＣａＯ ０ 〜１０ 重量％ ＳｒＯ ０ 〜１０ 重量％ ＢａＯ ３０ 〜４６ 重量％ ＺｎＯ ０ 〜１０ 重量％ ΣＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ４４ 〜６１ 重量％ Ｇｄ2 Ｏ3 ０．３〜 ５ 重量％ ＰｂＯ ０ 〜 ３ 重量％ Ｔａ2 Ｏ5 ０ 〜 ３ 重量％ ＷＯ3 ０ 〜 ３ 重量％ ＺｒＯ2 ０ 〜 ３ 重量％ ＴｉＯ2 ０ 〜 ３ 重量％ Ｐ2 Ｏ5 ８ 〜２２ 重量％ Ｆ2 −Ｏ １３ 〜１８ 重量％ Ｆ ２３ 〜３１ 重量％ を有し、必要に応じて通常の清澄剤を０．５重量％以下
含み、スペクトルＰg ,Fの青色領域で正の異常部分分散
を示し、１．４９＜ｎd ＜１．５４の屈折率、７１＜ν
d ＜８４のアッベ数、そして標準直線からの偏差△Ｐg
,F＞＋０．０２００を有し、結晶化安定性及び透過性に
優れた光学ガラスが提供される。In order to achieve the above-mentioned object, according to the present invention, the following composition SiO 2 0 to 2 wt% GeO 2 0 to 2 wt% ΣSiO 2 + GeO 2 0 to 2 wt% B 2 O 3 0 ~ 2 wt% Al 2 O 3 6 ~13.5 wt% Li 2 O 0-3 wt% Na 2 O 0-3 wt% K 2 O 0-3 wt% sigma alkali oxide 0-3 weight % MgO 0 to 10 wt% CaO 0 to 10 wt% SrO 0 to 10 wt% BaO 30 to 46 wt% ZnO 0 to 10 wt% ΣMgO + CaO + SrO + BaO + ZnO 44 to 61 wt% Gd 2 O 3 0.3 to 5 P 0 wt% to 3 wt% Ta 2 O 5 0 ~ 3 wt% WO 3 0 to 3 wt% ZrO 2 0 to 3 wt% TiO 2 0 to 3 wt% P 2 O 5 8 ~22 wt% F 2 -O 13 ~18 Has a volume% F 23 to 31% by weight, optionally containing conventional fining agent 0.5 wt% or less, the spectrum P g, shows a positive anomalous partial dispersion in the blue region of the F, 1.49 < Refractive index of n d <1.54, 71 <ν
Abbe number with d <84 and deviation from standard line ΔP g
, F > +0.0200, and an optical glass excellent in crystallization stability and transparency is provided.
【００１２】[0012]
【発明の作用及び態様】本発明のガラス系は、Ａｌ2 Ｏ
3 、ＢａＯ、Ｇｄ2 Ｏ3 、Ｐ2 Ｏ5 とフッ化物とで構成
される。Ａｌ2 Ｏ3 含量は６〜１３．５重量％である。
この範囲は、リン酸塩ガラスの相分離傾向ができるだけ
低く抑えられ、だが同時にＡｌ2 Ｏ3 成分が化学的耐久
性の向上に十分寄与し得るよう選定してある。Ａｌ2 Ｏ
3 成分は少なくとも６．９重量％であるのが好ましい。The glass system of the present invention is made of Al 2 O.
It is composed of 3 , BaO, Gd 2 O 3 , P 2 O 5 and a fluoride. The Al 2 O 3 content is 6 to 13.5% by weight.
This range is selected so that the phase separation tendency of the phosphate glass can be suppressed as low as possible, but at the same time, the Al 2 O 3 component can sufficiently contribute to the improvement of chemical durability. Al 2 O
Preferably, the three components are at least 6.9% by weight.
【００１３】ガラス系の第２の成分はＢａＯであり、そ
の割合は３０〜４６重量％である。ＢａＯは屈折率に大
いに寄与し、また標準直線からの相対部分分散の正の偏
差にも寄与する。さらに、ＢａＯ高含有ガラスは先行技
術に記載されたその他のアルカリ土類リン酸塩ガラスに
比べ失透に対しきわめて安定している。ＢａＯ含量は３
１．５〜４６重量％であるのが好ましい。The second glass-based component is BaO, in a proportion of 30 to 46% by weight. BaO contributes significantly to the refractive index and also to the positive deviation of the relative partial dispersion from the standard line. Furthermore, the BaO-rich glasses are extremely stable to devitrification compared to the other alkaline earth phosphate glasses described in the prior art. BaO content is 3
It is preferably from 1.5 to 46% by weight.
【００１４】ＢａＯの他になお別の、酸化亜鉛やＭｇ
Ｏ、ＣａＯ、ＳｒＯ等のアルカリ土類酸化物のような二
価酸化物も含有することができる。しかし、これら二価
酸化物の割合は１０重量％を越えるべきでない。ＭｇＯ
含量が１〜５重量％、ＣａＯ含量が４〜８重量％、Ｓｒ
Ｏ含量が４〜１０重量％、ＺｎＯ含量が０〜３重量％で
あるのが好ましい。二価酸化物ＭｇＯ、ＣａＯ、Ｓｒ
Ｏ、ＢａＯ、ＺｎＯの総含量は４４〜６１重量％とすべ
きである。この割合が６１重量％を超えると失透傾向が
増し、他方、４４重量％の値を下まわると標準直線から
の部分分散の求める正の偏差が達成されなくなる虞があ
る。In addition to BaO, zinc oxide and Mg
Divalent oxides such as alkaline earth oxides such as O, CaO, SrO can also be included. However, the proportion of these divalent oxides should not exceed 10% by weight. MgO
1-5% by weight, CaO content 4-8% by weight, Sr
It is preferable that the O content is 4 to 10% by weight and the ZnO content is 0 to 3% by weight. Divalent oxide MgO, CaO, Sr
The total content of O, BaO, ZnO should be 44-61% by weight. If this proportion exceeds 61% by weight, the devitrification tendency increases, while if it falls below the value of 44% by weight, the positive deviation required for the partial dispersion from the standard line may not be achieved.
【００１５】フッ化物イオンの含量は２３〜３１重量％
とすべきである。含有フッ化物は標準直線からの部分分
散の正方向偏差に大きく寄与し、但し失透傾向の上昇に
も寄与する。それ故、フッ化物の割合は３０重量％を越
えて高めないのが好ましい。The content of fluoride ion is 23 to 31% by weight
Should be. The contained fluoride greatly contributes to the positive deviation of the partial dispersion from the standard straight line, but also contributes to the increase of the devitrification tendency. Therefore, it is preferred that the proportion of fluoride does not rise above 30% by weight.
【００１６】更に別の重要なガラス成分はＧｄ2 Ｏ3 で
ある。これは所要の高屈折率を達成するのに役立ち、ガ
ラス形成傾向を損なうことなくガラス中に導入すること
ができる。酸化ガドリニウムは屈折率を高めるのに大き
く寄与し、正方向に偏差した高い部分分散を達成するう
えで本質的な役割を有する。この点でそれは、周知の如
く添加されるＬａ2 Ｏ3 とＹ2 Ｏ3 の作用をかなり凌駕
する。Ｇｄ2 Ｏ3 成分はさらに、肯定的作用として、混
合的に導入するフッ素化合物の含量又は溶融物中に現れ
る揮発性酸化フッ化物の含量を低く抑えることができ
る。酸化ガドリニウム含量は０．３〜５重量％とすべき
である。Ｇｄ2 Ｏ3 は価格が高いので０．３〜３重量％
の含量が好ましい。Yet another important glass component is Gd 2 O 3 . This helps achieve the required high index of refraction and can be incorporated into the glass without compromising the glass forming tendency. Gadolinium oxide greatly contributes to increasing the refractive index and has an essential role in achieving a positive partial deviation and high partial dispersion. In this respect it far exceeds the action of La 2 O 3 and Y 2 O 3 which are added in a known manner. As a positive effect, the Gd 2 O 3 component can also keep the content of fluorine compounds introduced mixedly or the content of volatile oxyfluoride compounds present in the melt low. The gadolinium oxide content should be 0.3-5% by weight. Gd 2 O 3 is expensive, so 0.3-3% by weight
Is preferred.
【００１７】リン酸塩は、Ｐ2 Ｏ5 として計算して、ガ
ラス中に８〜２２重量％の量存在すべきである。それは
網状結合剤として働く。上限を越えると失透安定性が高
まるのではあるが、しかし求める光学特性をもはや達成
することができなくなる。Ｐ2 Ｏ5 分が８重量％を下ま
わると、この網状結合剤の割合が過度に少ないのでガラ
スの失透傾向が高まる。The phosphate should be present in the glass in an amount of 8 to 22% by weight, calculated as P 2 O 5 . It acts as a reticulate binder. If the upper limit is exceeded, the devitrification stability will increase, but the desired optical properties will no longer be achieved. When the P 2 O 5 content is less than 8% by weight, the devitrification tendency of the glass is increased because the proportion of the network binder is excessively small.
【００１８】ＳｉＯ2 、ＧｅＯ2 、Ｂ2 Ｏ3 はそれぞれ
２重量％以下の微量でガラス中に問題なく存在すること
ができるが、しかしＳｉＯ2 とＧｅＯ2 との総和が２重
量％を超えるべきでない。これら３つの酸化物を微量に
制限することが必要となるのは、これら酸化物の割合が
高くなるとガラスの相分離傾向が著しく高まることがあ
るからである。それ故、ＳｉＯ2 、ＧｅＯ2 、Ｂ2 Ｏ3
を全く省き、せいぜい０〜２重量％の微量のＧｅＯ2 を
許すのが好ましい。というのも、前記３成分のこれらの
成分は、ごく僅かではあってもなお相分離傾向に影響す
るからである。[0018] SiO 2, GeO 2, B 2 O 3 is able to exist without problems in the glass with 2% by weight of trace respectively, but should sum of SiO 2 and GeO 2 exceeds 2 wt% Not. The reason why it is necessary to limit the amounts of these three oxides to a very small amount is that when the proportion of these oxides is increased, the tendency of phase separation of glass may be significantly increased. Therefore, SiO 2 , GeO 2 , B 2 O 3
It is preferable to completely omit the above and allow a trace amount of GeO 2 of at most 0 to 2% by weight. This is because these components of the above three components still influence the phase separation tendency, albeit only slightly.
【００１９】ガラスはさらに、ガラスの溶融性向上のた
め、そして溶融に起因する屈折率変動を補償できるよう
にするため、合計３重量％までの量のアルカリ酸化物を
含むことができる。アルカリ酸化物としては、まずなに
よりも酸化リチウム、酸化ナトリウム、酸化カリウムが
それぞれ３重量％以下の量で使用される。しかし、好ま
しくはガラスが酸化ナトリウムを含有せず、また酸化カ
リウム含量は０．５重量％を超えないことが好ましい。
ガラスはさらになお、ＰｂＯを０〜３重量％の量、Ｔａ
2 Ｏ5 を０〜３重量％の量、ＷＯ3 を０〜３重量％の
量、ＺｒＯ2 を０〜３重量％の量、ＴｉＯ2 を０〜３重
量％の量で含有することができる。しかし、ＰｂＯ、Ｗ
Ｏ3 の割合がそれぞれ２重量％を超えず、ＺｒＯ2 とＴ
ｉＯ2 の割合を全く省くのが好ましい。The glass may further contain alkali oxides in a total amount of up to 3% by weight, in order to improve the meltability of the glass and to be able to compensate for the refractive index variations due to melting. As the alkali oxide, lithium oxide, sodium oxide, and potassium oxide are used in an amount of 3% by weight or less. However, it is preferred that the glass does not contain sodium oxide and the potassium oxide content does not exceed 0.5% by weight.
The glass still further contains 0-3% by weight of PbO, Ta
2 O 5 may be contained in an amount of 0 to 3% by weight, WO 3 in an amount of 0 to 3% by weight, ZrO 2 in an amount of 0 to 3% by weight, and TiO 2 in an amount of 0 to 3% by weight. . However, PbO, W
The proportion of O 3 does not exceed 2% by weight, and ZrO 2 and T
It is preferable to omit the proportion of iO 2 altogether.
【００２０】特に好ましいガラスは、その組成が酸化物
基準でＢａＯ：３０〜４６重量％、ＭｇＯ：１〜５重量
％、ＣａＯ：４〜８重量％、ＳｒＯ：４〜１０重量％、
ＺｎＯ：０〜３重量％、ΣＭｇＯ＋ＣａＯ＋ＳｒＯ＋Ｂ
ａＯ＋ＺｎＯ：４４〜６１重量％、ＧｅＯ2 ：０〜２重
量％、Ａｌ2 Ｏ3 ：６〜１３．５重量％、Ｌｉ2 Ｏ：０
〜３重量％、Ｋ2 Ｏ：０〜０．５重量％、ΣＬｉ2 Ｏ＋
Ｋ2 Ｏ：０〜３重量％、Ｇｄ2 Ｏ3 ：０．３〜３重量
％、ＰｂＯ：０〜２重量％、Ｔａ2 Ｏ5 ：０〜３重量
％、ＷＯ3 ：０〜２重量％、Ｐ2 Ｏ5 ：８〜２２重量
％、Ｆ2 ：２３〜３１重量％、Ｆ2 −Ｏ：１３〜１８重
量％である。ガラスのさらなる向上は、Ａｌ2Ｏ3 を少
なくとも６．９重量％の量、ＢａＯを少なくとも３１．
５重量％の量、Ｆを最高３０重量％（Ｆ2 −Ｏの１７．
２重量％に相当）の量で使用することによって達成する
ことができる。Particularly preferred glass has a composition of BaO: 30 to 46% by weight, MgO: 1 to 5% by weight, CaO: 4 to 8% by weight, SrO: 4 to 10% by weight, based on oxides.
ZnO: 0 to 3% by weight, ΣMgO + CaO + SrO + B
aO + ZnO: 44~61 wt%, GeO 2: 0~2 wt%, Al 2 O 3: 6~13.5 wt%, Li 2 O: 0
3 wt%, K 2 O: 0~0.5 wt%, ΣLi 2 O +
K 2 O: 0 to 3 wt%, Gd 2 O 3: 0.3~3 wt%, PbO: 0 to 2 wt%, Ta 2 O 5: 0~3 wt%, WO 3: 0 to 2 wt% , P 2 O 5: 8~22 wt%, F 2: 23 to 31 wt%, F 2 -O: 13~18 by weight. A further improvement of the glass is that Al 2 O 3 in an amount of at least 6.9% by weight and BaO at least 31.
5% by weight, F up to 30 wt% (F 2 -O 17.
2% by weight).
【００２１】必要に応じて、ガラスはさらに通常の清澄
剤、例えばＡｓ2 Ｏ3 、Ｓｂ2 Ｏ3、ＣｅＯ2 を約０．
５重量％までの量、そして硝酸塩と硫酸塩を含有するこ
とができる。清澄剤は、この範囲の使用量の場合、正方
向に偏差した部分分散に影響しない。If desired, the glass may also be supplemented with conventional fining agents such as As 2 O 3 , Sb 2 O 3 , CeO 2 to about 0.
It can contain up to 5% by weight, and also nitrates and sulphates. The fining agent has no effect on the partial deviation deviated in the positive direction in the use amount in this range.
【００２２】[0022]
【実施例】以下、実施例を示して本発明の効果について
具体的に示すが、本発明が下記実施例に限定されるもの
でないことはもとよりである。EXAMPLES Hereinafter, the effects of the present invention will be specifically shown by showing Examples, but it goes without saying that the present invention is not limited to the following Examples.
【００２３】ガラスの製造は、計算した原料（酸化物、
リン酸塩、フッ化物、炭酸塩等）を十分に混合し、約９
００℃で溶解し、次に清澄し十分に均質化する形で行っ
た。鋳造は予熱した鋳型内で約８００℃で行った。例示
的に溶解した９種類のガラスの組成と特性を表１に示
す。なお、ガラスの組成は酸化物に対する重量％で記載
してあり、導入したフッ化物イオンの割合は個々の溶融
物を比較し易くするためＦ2 −Ｏ成分としても記載して
ある。The glass is manufactured by calculating the raw materials (oxide,
(Phosphate, fluoride, carbonate, etc.) should be mixed thoroughly and
It was carried out in the form of melting at 00 ° C., then clarification and thorough homogenization. Casting was performed at about 800 ° C. in a preheated mold. Table 1 shows the compositions and properties of the nine types of glass melted by way of example. The composition of the glass is described by weight% with respect to the oxide, and the ratio of the introduced fluoride ions is also described as the F 2 —O component in order to make it easy to compare the individual melts.
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】上記表１に示す結果からも明らかなよう
に、本発明の光学ガラスは、スペクトルＰg ,Fの青色領
域で正の異常部分分散を示し、１．４９＜ｎd ＜１．５
４の屈折率、７１＜νd ＜８４のアッベ数、そして標準
直線からの偏差△Ｐg ,F＞＋０．０２を有し、結晶化安
定性及び透過性に優れている。また、本発明の光学ガラ
スは、光学特性がきわめて良好であるだけでなく、その
製造が特殊な原料に拘束されることがなく、所要のリン
酸塩成分及び／又はフッ化物イオン成分を任意の原料組
合せにより導入することができる点も特徴としている。
これにより、ガラスを工業的に製造する場合、使用原料
の融通性によって諸利点が得られる。As is clear from the results shown in Table 1 above, the optical glass of the present invention exhibits positive anomalous partial dispersion in the blue region of the spectrum P g , F , and 1.49 <n d <1. .5
It has a refractive index of 4, an Abbe number of 71 <ν d <84, and a deviation ΔP g , F > +0.02 from the standard line, and is excellent in crystallization stability and transparency. Further, the optical glass of the present invention not only has extremely good optical characteristics, but its production is not restricted by a special raw material, and the required phosphate component and / or fluoride ion component can be arbitrarily added. Another feature is that it can be introduced by combining raw materials.
As a result, when glass is industrially produced, various advantages are obtained due to the flexibility of the raw materials used.
フロントページの続き (56)参考文献 特開 平２−149445（ＪＰ，Ａ) 特開 平２−124740（ＪＰ，Ａ) 特開 昭54−129016（ＪＰ，Ａ) 特公 昭52−43852（ＪＰ，Ｂ１) 特表 平３−500162（ＪＰ，Ａ)Continuation of the front page (56) Reference JP-A-2-149445 (JP, A) JP-A-2-124740 (JP, A) JP-A-54-129016 (JP, A) JP-B-52-43852 (JP , B1) Special table: 3-500162 (JP, A)
Claims (5)
含み、スペクトルＰg ,Fの青色領域で正の異常部分分散
を示し、１．４９＜ｎd ＜１．５４の屈折率、７１＜ν
d ＜８４のアッベ数、そして標準直線からの偏差△Ｐg
,F＞＋０．０２００を有し、結晶化安定性及び透過性に
優れた光学ガラス。1. The following composition: SiO 2 0 to 2% by weight GeO 2 0 to 2% by weight ΣSiO 2 + GeO 2 0 to 2% by weight B 2 O 3 0 to 2% by weight Al 2 O 3 6 to 13.5% by weight % Li 2 O 0-3 wt% Na 2 O 0-3 wt% K 2 O 0-3 wt% sigma alkali oxide 0-3 wt% MgO 0 to 10 wt% CaO 0 to 10 wt% SrO 0 to 10 % By weight BaO 30 to 46% by weight ZnO 0 to 10% by weight ΣMgO + CaO + SrO + BaO + ZnO 44 to 61% by weight Gd 2 O 3 0.3 to 5% by weight PbO 0 to 3% by weight Ta 2 O 5 0 to 3% by weight WO 3 3% by weight ZrO 2 0 to 3% by weight TiO 2 0 to 3% by weight P 2 O 5 8 to 22% by weight F 2 —O 13 to 18% by weight F 23 to 31% by weight and, if necessary, usually Qing of Agent comprises 0.5 wt% or less, the spectrum P g, shows a positive anomalous partial dispersion in the blue region of the F, 1.49 <refractive index of n d <1.54, 71 <ν
Abbe number with d <84 and deviation from standard line ΔP g
, F > +0.0200, which is an optical glass having excellent crystallization stability and transparency.
含むことを特徴とする請求項１に記載のガラス。2. The following composition: GeO 2 0 to 2% by weight Al 2 O 3 6 to 13.5% by weight Li 2 O 0 to 3% by weight K 2 O 0 to 0.5% by weight ΣLi 2 O + K 2 O 0 3% by weight MgO 1 to 5% by weight CaO 4 to 8% by weight SrO 4 to 10% by weight BaO 30 to 46% by weight ZnO 0 to 3% by weight ΣMgO + CaO + SrO + BaO + ZnO 44 to 61 3 % by weight Gd 2 O % PbO 0 ~ 2 wt% Ta 2 O 5 0 ~ 3 wt% WO 3 0 ~ 2 wt% P 2 O 5 8 ~22 wt% F 2 -O 13 has to 18 wt% F 23 to 31 wt% The glass according to claim 1, further comprising a normal fining agent in an amount of 0.5% by weight or less, if necessary.
％であることを特徴とする請求項１又は２に記載のガラ
ス。3. The glass according to claim 1, wherein the Al 2 O 3 content is 6.9 to 13.5% by weight.
ることを特徴とする請求項１乃至３のいずれか一項に記
載のガラス。4. The glass according to claim 1, which has a BaO content of 31.5 to 46% by weight.
特徴とする請求項１乃至４のいずれか一項に記載のガラ
ス。5. The glass according to claim 1, wherein the F content is 23 to 30% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4132258.4 | 1991-09-27 | ||
| DE19914132258 DE4132258C1 (en) | 1991-09-27 | 1991-09-27 | Optical glass - contg. oxide(s) of silicon, germanium, boron, aluminium, zinc, magnesium, sodium, potassium, lithium, strontium, barium, calcium, gadolinium, tantalum, lead, etc. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05208842A JPH05208842A (en) | 1993-08-20 |
| JP2515672B2 true JP2515672B2 (en) | 1996-07-10 |
Family
ID=6441661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4240070A Expired - Fee Related JP2515672B2 (en) | 1991-09-27 | 1992-08-18 | Optical glass showing positive anomalous partial dispersion in the blue region |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2515672B2 (en) |
| DE (1) | DE4132258C1 (en) |
| FR (1) | FR2681854B1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19924520C1 (en) * | 1999-05-28 | 2000-06-21 | Schott Glas | Lead-free optical borosilicate glass, especially for high performance optics, contains aluminum, calcium and tantalum oxides and has a high negative anomalous partial dispersion |
| JP5491686B2 (en) * | 2006-09-07 | 2014-05-14 | 株式会社オハラ | Glass |
| JP5410270B2 (en) * | 2007-03-06 | 2014-02-05 | Ｈｏｙａ株式会社 | Optical glass, press-molding preform, optical element and manufacturing method thereof |
| JP2009256149A (en) * | 2008-04-18 | 2009-11-05 | Hoya Corp | Optical glass, method of producing the same, optical element and method of producing optical element |
| JP5188269B2 (en) | 2008-05-30 | 2013-04-24 | Ｈｏｙａ株式会社 | Optical glass, glass material for press molding, optical element blank, optical element, and production method thereof |
| JP2010059021A (en) * | 2008-09-04 | 2010-03-18 | Hoya Corp | Fluorophosphate glass, glass base material for press forming, optical element blank, optical element and method of producing them |
| JP6055545B2 (en) * | 2013-06-04 | 2016-12-27 | Hoya株式会社 | Optical glass, optical element blank, press-molding glass material, optical element, and method for producing the same |
| JP6143706B2 (en) * | 2014-04-25 | 2017-06-07 | 株式会社オハラ | Optical glass, optical element and preform |
| JP6825939B2 (en) * | 2017-03-02 | 2021-02-03 | Hoya株式会社 | Optical glass and optical elements |
| JP7392724B2 (en) * | 2019-08-06 | 2023-12-06 | 株式会社ニコン | Optical glass, optical elements, optical systems, interchangeable lenses and optical devices |
| JP7090678B2 (en) * | 2020-10-28 | 2022-06-24 | Hoya株式会社 | Optical glass and optical elements |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60171244A (en) * | 1984-02-16 | 1985-09-04 | Ohara Inc | Optical glass |
| JPS60221338A (en) * | 1984-04-12 | 1985-11-06 | Ohara Inc | Optical glass |
| JP2616983B2 (en) * | 1988-12-01 | 1997-06-04 | 株式会社住田光学ガラス | Fluorate optical glass |
-
1991
- 1991-09-27 DE DE19914132258 patent/DE4132258C1/en not_active Expired - Lifetime
-
1992
- 1992-08-18 JP JP4240070A patent/JP2515672B2/en not_active Expired - Fee Related
- 1992-09-25 FR FR9211482A patent/FR2681854B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4132258C1 (en) | 1992-11-12 |
| JPH05208842A (en) | 1993-08-20 |
| FR2681854A1 (en) | 1993-04-02 |
| FR2681854B1 (en) | 1995-06-09 |
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