JP3238740B2 - Optical glass - Google Patents
Optical glassInfo
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- JP3238740B2 JP3238740B2 JP09175092A JP9175092A JP3238740B2 JP 3238740 B2 JP3238740 B2 JP 3238740B2 JP 09175092 A JP09175092 A JP 09175092A JP 9175092 A JP9175092 A JP 9175092A JP 3238740 B2 JP3238740 B2 JP 3238740B2
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- chemical durability
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- optical glass
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＳｉＯ2−Ｂ2Ｏ3−Ｌ
ａ2Ｏ3−ＴｉＯ2−Ｎｂ2Ｏ5−ＣａＯ−ＢａＯ−Ｌｉ2Ｏ
系の組成を有し、屈折率（Ｎｄ）が約１．６４〜１．７
９、およびアッベ数（νｄ）が約３５〜５８の範囲の光
学恒数を示し、かつ優れた化学的耐久性と溶融性を有す
る新規な光学ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an SiO 2 -B 2 O 3 -L
a 2 O 3 -TiO 2 -Nb 2 O 5 -CaO-BaO-Li 2 O
It has a system composition and has a refractive index (Nd) of about 1.64 to 1.7.
The present invention relates to a novel optical glass having an optical constant of 9 and an Abbe number (νd) in the range of about 35 to 58, and having excellent chemical durability and melting property.
【０００２】[0002]
【従来の技術】従来から、前記の光学恒数を有するガラ
スは種々知られており、例えば特公昭３８−５０１２号
公報には、二価金属酸化物成分を多量に含有するＳｉＯ
2−Ｂ2Ｏ3−Ｌａ2Ｏ3−Ａｌ2Ｏ3−ＺｒＯ2−ＴｉＯ2−
ＢａＯ−ＣａＯ−ＺｎＯ系ガラスが開示されている。し
かし、このガラスは、化学的耐久性が良好ではない。ま
た、特開昭５３−７５２１０号公報には、ＢａＯを多量
に含有するＳｉＯ2−Ｂ2Ｏ3−Ｌａ2Ｏ3−ＺｒＯ2−Ｔｉ
Ｏ2−ＢａＯ−ＺｎＯ系ガラスが開示されているが、こ
のガラスは、溶融性は良好であるが、化学的耐久性が良
いとは言えない。2. Description of the Related Art Conventionally, various glasses having the above-mentioned optical constants have been known. For example, Japanese Patent Publication No. 38-5012 discloses a SiO.sub.
2 -B 2 O 3 -La 2 O 3 -Al 2 O 3 -ZrO 2 -TiO 2 -
A BaO-CaO-ZnO-based glass is disclosed. However, this glass does not have good chemical durability. Further, in JP-A-53-75210, SiO 2 -B 2 O 3 -La 2 O 3 -ZrO 2 -Ti it is containing a large amount of BaO
Although an O 2 —BaO—ZnO-based glass is disclosed, this glass has good melting properties but cannot be said to have good chemical durability.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
従来のガラスにみられる欠点を解消し、溶融性に優れて
おり、しかも、化学的耐久性が改善された光学ガラスを
提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an optical glass which solves the above-mentioned drawbacks of the conventional glass, is excellent in meltability, and has improved chemical durability. It is in.
【０００４】[0004]
【課題を解決するための手段】上記目的を達成するた
め、本発明者等は、鋭意試験研究を重ねた結果、従来、
具体的に開示されていない特定組成範囲のＳｉＯ2−Ｂ2
Ｏ3−Ｌａ2Ｏ3−ＴｉＯ2−Ｎｂ2Ｏ5−ＣａＯ−ＢａＯ−
Ｌｉ2Ｏ系ガラスにおいて、前記光学恒数を有し、か
つ、優れた化学的耐久性と溶融性を有するガラスが得ら
れることをみいだし、本発明をなすに至った。Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive tests and studies, and as a result,
SiO 2 —B 2 of specific composition range not specifically disclosed
O 3 —La 2 O 3 —TiO 2 —Nb 2 O 5 —CaO—BaO—
The present inventors have found that a glass having the above-mentioned optical constants and excellent chemical durability and melting property can be obtained in Li 2 O-based glass, and the present invention has been accomplished.
【０００５】前記の目的を達成する本発明の光学ガラス
の組成の特徴は、重量％で、ＳｉＯ2 １４〜３５％、
Ｂ2Ｏ3 ６．５〜２３．５％、Ｌａ2Ｏ3 ２３．５〜４
０％、ＴｉＯ2 ０．２〜７．５％、Ｎｂ2Ｏ5 ０．２
〜１０％、ただし、ＴｉＯ2＋Ｎｂ2Ｏ5 ０．５〜１５
％、Ａｌ2Ｏ3 ０〜５％、ＺｒＯ2 ０〜１０％、Ｔａ2
Ｏ5 ０〜５％、ＷＯ3 ０〜５％、ＺｎＯ ０〜１０
％、ＭｇＯ ０〜１０％、ＣａＯ ７〜１４％、ＳｒＯ
０〜２０％、ＢａＯ ５．５〜２４．５％、Ｌｉ2Ｏ
０．１〜３．３％、Ｎａ2Ｏ＋Ｋ2Ｏ ０〜５％、Ａｓ2
Ｏ3＋Ｓｂ2Ｏ3 ０〜１％、および上記各金属元素の１
種または２種以上の酸化物の一部または全部と置換した
弗化物のＦ2としての合計量０〜５％を含有するところ
にある。[0005] A feature of the composition of the optical glass of the present invention to achieve the object of, by weight%, SiO 2 14-35%,
B 2 O 3 6.5~23.5%, La 2 O 3 23.5~4
0%, TiO 2 0.2-7.5%, Nb 2 O 5 0.2
TiO 2 + Nb 2 O 5 0.5 to 15%
%, Al 2 O 3 0~5% , ZrO 2 0~10%, Ta 2
O 5 0~5%, WO 3 0~5 %, ZnO 0~10
%, MgO 0-10%, CaO 7-14%, SrO
0~20%, BaO 5.5~24.5%, Li 2 O
0.1~3.3%, Na 2 O + K 2 O 0~5%, As 2
O 3 + Sb 2 O 3 0 to 1%, and 1 of each of the above metal elements
There is to contain the total amount 0-5% of the F 2 of part or all the substituted fluoride species or two or more oxides.
【０００６】上記各成分の組成範囲を限定した理由は、
つぎのとおりである。すなわち、ＳｉＯ2成分の量は１
４％未満であるとガラスの化学的耐久性が低下し、また
その量が３５％を超えるとガラスの溶融性が悪化すると
共に本発明の目標とする光学恒数を維持できなくなる。
Ｂ2Ｏ3成分の量が６．５％未満であると、ガラス溶融の
際、粘度が増大して均質なガラスを得難くなり、またそ
の量が２３．５％を超えるとガラスの化学的耐久性が低
下する。Ｌａ2Ｏ3成分は、本発明のガラスにおいて目標
とする光学恒数を維持させつつ、耐失透性を向上させる
ため必要であるが、その量が２３．５％未満であると、
ガラスの屈折率または耐失透性が低下し、また４０％を
超えるとガラスはかえって失透しやすくなる。The reasons for limiting the composition ranges of the above components are as follows.
It is as follows. That is, the amount of the SiO 2 component is 1
If the amount is less than 4%, the chemical durability of the glass is reduced, and if the amount exceeds 35%, the melting property of the glass is deteriorated and the optical constants targeted by the present invention cannot be maintained.
If the amount of the B 2 O 3 component is less than 6.5%, the viscosity increases during melting of the glass, making it difficult to obtain a homogeneous glass. If the amount exceeds 23.5%, the chemical content of the glass is reduced. The durability decreases. The La 2 O 3 component is necessary to improve the devitrification resistance while maintaining the target optical constants in the glass of the present invention, but if the amount is less than 23.5%,
If the refractive index or the devitrification resistance of the glass is reduced, and if it exceeds 40%, the glass is more likely to be devitrified.
【０００７】ＴｉＯ2およびＮｂ2Ｏ5の両成分は、ガラ
スの屈折率を高め、かつ化学的耐久性を向上させる効果
があるが、それらの量がそれぞれ０．２％未満では上記
効果が十分でなく、またＴｉＯ2成分は７．５％を、Ｎ
ｂ2Ｏ5成分は１０％を各々超えるとガラスの耐失透性お
よび光線透過率が悪化する。また、これらの成分の合計
量は、上記効果を得るため０．５％以上必要であり、ま
た１５％を超えると、ガラスの耐失透性および光線透過
率が悪化する。Ａｌ2Ｏ3およびＺｒＯ2の各成分は、屈
折率の調整および化学的耐久性の改善に有効であるが、
それらの量が各々５％および１０％を超えるとガラスの
溶融性および耐失透性が悪化する。Ｔａ2Ｏ5およびＷＯ
3の各成分は、屈折率を高め、かつ化学的耐久性を改善
するため必要に応じ添加し得るが、それらの量は各々５
％以下で十分である。[0007] Both components of TiO 2 and Nb 2 O 5 have the effect of increasing the refractive index of glass and improving the chemical durability. However, if their amounts are less than 0.2%, the above effects are not sufficient. But the TiO 2 component is 7.5% N
b 2 O 5 component are each greater than the glass devitrification resistance and light transmittance is deteriorated 10%. Further, the total amount of these components is required to be 0.5% or more in order to obtain the above effects, and if it exceeds 15%, the devitrification resistance and light transmittance of the glass deteriorate. Each component of Al 2 O 3 and ZrO 2 is effective for adjusting the refractive index and improving the chemical durability.
If their amounts exceed 5% and 10%, respectively, the melting property and the devitrification resistance of the glass deteriorate. Ta 2 O 5 and WO
Each of the components ( 3 ) can be added as needed to increase the refractive index and improve the chemical durability, but their amounts are each 5
% Or less is sufficient.
【０００８】ＺｎＯおよびＭｇＯの各成分は、光学恒数
の調整および溶融性の改善のため、任意に添加し得る
が、それらの量が各々１０％を超えると、ガラスの耐失
透性が悪化する。ＣａＯ成分は、光学恒数の調整および
化学的耐久性の向上のため重要な成分であるが、その量
が７％未満ではこれらの効果は十分でなく、また１４％
を超えるとガラスの耐失透性が悪くなる。ＳｒＯ成分
は、光学恒数の調整および耐失透性の改善に有効である
が、その量が２０％を超えると、ガラスの化学的耐久性
が悪化する。ＢａＯ成分は、ガラスの失透傾向を防止
し、所望の光学恒数を維持させる効果があるが、その量
が５．５％未満ではこれらの効果が十分でなく、また２
４．５％を超えるとガラスの化学的耐久性が低下する。Each component of ZnO and MgO can be arbitrarily added to adjust the optical constants and improve the melting property. However, if their amounts exceed 10%, the devitrification resistance of the glass deteriorates. I do. The CaO component is an important component for adjusting the optical constants and improving the chemical durability. However, if its amount is less than 7%, these effects are not sufficient, and 14%
If it exceeds 300, the devitrification resistance of the glass deteriorates. The SrO component is effective for adjusting the optical constants and improving the devitrification resistance, but if its amount exceeds 20%, the chemical durability of the glass deteriorates. The BaO component has the effect of preventing the glass from devitrifying and maintaining a desired optical constant. However, if the amount is less than 5.5%, these effects are not sufficient.
If it exceeds 4.5%, the chemical durability of the glass decreases.
【０００９】Ｌｉ２Ｏ成分は、ガラスの溶融性を改善す
るとともにガラスの化学的耐久性を良くする効果があ
り、その量が０．１％未満ではこれらの効果が充分でな
く、また３．３％を超えるとガラスの耐失透性が悪化す
る。Na２OおよびK２Oの各成分は、ガラスの溶融性を改
善する効果があるが、これらの成分の１種または２種の
合計量が５％を超えるとガラスの化学的耐久性が悪化す
る。As２O３およびSb２O３の各成分は、ガラス溶融の際
の清澄剤として任意に添加し得るが、これらの成分の１
種または２種の合計量は、１％以内で充分である。な
お、本発明のガラスに上記以外の成分、例えばRb２O、C
s２O、GeO２、P２O５、PbO、Gd ２ O ３ およびBi２O３等の
成分を合計で５％程度まで、ガラスの光学恒数の調整ま
たは溶融性の改善等のため、必要に応じ添加してもさし
つかえない。The Li 2 O component has the effect of improving the melting property of the glass and improving the chemical durability of the glass. If the amount is less than 0.1%, these effects are not sufficient. If it exceeds 3%, the devitrification resistance of the glass deteriorates. Each component of Na 2 O and K 2 O has an effect of improving the melting property of the glass, but when the total amount of one or two of these components exceeds 5%, the chemical durability of the glass deteriorates. I do. Each component of As 2 O 3 and Sb 2 O 3 can be arbitrarily added as a fining agent during glass melting.
A total amount of one or two species of less than 1% is sufficient. In addition, components other than the above, for example, Rb 2 O, C
Components such as s 2 O, GeO 2 , P 2 O 5 , PbO, Gd 2 O 3 and Bi 2 O 3 up to a total of about 5%, for adjusting the optical constants of the glass or improving the melting property, etc. It can be added as needed.
【００１０】[0010]
【実施例】つぎに、本発明の光学ガラスにかかる好適な
実施組成例（Ｎｏ．１〜Ｎｏ．１０）および前記従来の
ガラスの比較組成例（Ｎｏ．ＡおよびＮｏ．Ｂ）を、こ
れらのガラスの光学恒数（Ｎｄ、νｄ）および耐酸性
（ＳＲ）数値とともに表１に示した。なお、上記ＳＲ値
は、国際標準化機構ＩＳＯ８４２４：１９８７（Ｅ）の
測定方法に準拠し測定して得た結果を表したものであ
る。ここで、ＳＲ値は、所定の酸処理液中におけるガラ
ス試料が０．１μｍの侵食を受けるのに要した時間
（ｈ）によって等級付けしたものである。ＳＲ値＝４お
よび５の場合は、ｐＨ０．３の硝酸溶液を用いそれぞれ
０．１〜１ｈおよび０．１ｈ以下を要したことを示す。
また、ＳＲ値＝５、５１、５２および５３の場合は、い
ずれもｐＨ４．６の酢酸緩衝液を用い、それぞれ１０ｈ
以上、１〜１０ｈ、０．１〜１ｈおよび０．１ｈ以下を
要したことを示している。EXAMPLES Next, preferred composition examples (No. 1 to No. 10) of the optical glass of the present invention and comparative composition examples (No. A and No. B) of the conventional glass will be described. The results are shown in Table 1 together with the optical constants (Nd, νd) and acid resistance (SR) of the glass. In addition, the said SR value represents the result obtained by measuring based on the measuring method of International Organization for Standardization ISO8424: 1987 (E). Here, the SR value is graded according to the time (h) required for a glass sample in a predetermined acid treatment liquid to undergo erosion of 0.1 μm. When the SR value is 4 or 5, it indicates that a nitric acid solution having a pH of 0.3 requires 0.1 to 1 h and 0.1 h or less, respectively.
In the case of SR values of 5, 51, 52 and 53, an acetate buffer of pH 4.6 was used for 10 hours each.
As described above, 1 to 10 h, 0.1 to 1 h, and 0.1 h or less are required.
【００１１】[0011]
【表１】 [Table 1]
【表１】 [Table 1]
【表１】 [Table 1]
【表１】 [Table 1]
【００１２】表１にみられるとおり、本発明の実施組成
例のガラスＮｏ．９およびＮｏ．１０は、それぞれほぼ
同等の光学恒数を有する比較組成例のガラスＮｏ．Ａお
よびＮｏ．Ｂと比較すると、いずれもＳＲ値が向上し、
一段と優れた化学的耐久性を示している。本発明の他の
実施組成例のガラスも同様に優れたＳＲ値を示してい
る。また、本発明の上記実施組成例のガラスは、炭酸
塩、硝酸塩および酸化物等の通常の光学ガラス用原料を
秤量混合し、これを白金坩堝等を用い、約１１００〜１
３００℃、約２〜５時間で溶融脱泡し、攪拌均質化した
後、金型に鋳込み徐冷することにより得られるが、同等
の光学恒数を有する従来のガラスに比べ、いずれも約５
０〜１５０℃低温で脱泡清澄化させることができるので
有利である。As can be seen from Table 1, the glass No. of the working composition of the present invention has the following composition. 9 and No. 9 Glass Nos. 10 of Comparative Composition Examples each having substantially the same optical constants. A and No. Compared with B, the SR value is improved
It shows much better chemical durability. The glasses of the other composition examples of the present invention also show excellent SR values. In addition, the glass of the above-mentioned composition example of the present invention is prepared by weighing and mixing ordinary optical glass materials such as carbonates, nitrates and oxides, and using a platinum crucible or the like for about 1100 to 1
It is obtained by melting and defoaming at 300 ° C. for about 2 to 5 hours, stirring and homogenizing, and then casting it into a mold and slowly cooling it.
This is advantageous because the defoaming and fining can be performed at a low temperature of 0 to 150 ° C.
【００１３】[0013]
【発明の効果】上述の通り、本発明の光学ガラスは、特
定組成範囲のＳｉＯ2−Ｂ2Ｏ3−Ｌａ2Ｏ3−ＴｉＯ2−Ｎ
ｂ2Ｏ5−ＣａＯ−ＢａＯ−Ｌｉ2Ｏ系ガラスであり、従
って屈折率（Ｎｄ）が約１．６４〜１．７９およびアッ
ベ数（νｄ）が約３５〜５８の範囲の光学恒数を有し、
しかも従来のガラスに比べて、化学的耐久性に優れ、ま
た溶融性も良好であって、量産性に優れている。As described above, the optical glass of the present invention has a specific composition range of SiO 2 —B 2 O 3 —La 2 O 3 —TiO 2 —N
b 2 O 5 —CaO—BaO—Li 2 O-based glass, and therefore has an optical constant having a refractive index (Nd) of about 1.64 to 1.79 and an Abbe number (νd) of about 35 to 58. Have
Moreover, as compared with conventional glass, it has excellent chemical durability, good melting property, and excellent mass productivity.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−221338（ＪＰ，Ａ) 特開 昭54−3115（ＪＰ，Ａ) 特開 昭62−100449（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C03C 1/00 - 14/00 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-60-221338 (JP, A) JP-A-54-3115 (JP, A) JP-A-62-100449 (JP, A) (58) Field (Int.Cl. 7 , DB name) C03C 1/00-14/00
Claims (2)
一部または全部と置換した弗化物のF２としての合計量
０〜５％を含有し、Ｙ ２ O ３ を含有せず、ＳＲ値が４、
５または５１であることを特徴とする光学ガラス。(1) SiO 2 14 to 35% B 2 O 3 6.5 to 23.5% La 2 O 3 23.5 to 40% TiO 2 0.2 to 7.5% Nb 2 O by weight% 5 from 0.2 to 10% provided that TiO 2 + Nb 2 O 5 0.5~15 % Al 2 O 3 0 ~ 5% ZrO 2 0 ~10% Ta 2 O 5 0 ~ 5% WO 3 0 ~ 5% ZnO 0 -10% MgO 0 -10% CaO 7 -14% SrO 0 -20% BaO 5.5-24.5% Li 2 O 0.1-3.3% Na 2 O + K 2 O 0 -5% As 2 O 3 + Sb 2 O 3 0 to 1%, and a total of 0 to 5% of fluoride as a F 2 substituted with a part or all of one or more kinds of oxides of the above metal elements as Y 2. Contains no 2 O 3 and has an SR value of 4,
An optical glass characterized by being 5 or 51 .
約２〜５時間で溶融脱泡し、徐冷することによって得ら
れることを特徴とする、請求項１記載の光学ガラス。2. The method according to claim 1, wherein the glass material is heated to about 1100 to 1300 ° C.
The optical glass according to claim 1 , wherein the optical glass is obtained by melting and defoaming in about 2 to 5 hours and slowly cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09175092A JP3238740B2 (en) | 1992-03-17 | 1992-03-17 | Optical glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09175092A JP3238740B2 (en) | 1992-03-17 | 1992-03-17 | Optical glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05262533A JPH05262533A (en) | 1993-10-12 |
| JP3238740B2 true JP3238740B2 (en) | 2001-12-17 |
Family
ID=14035216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09175092A Expired - Lifetime JP3238740B2 (en) | 1992-03-17 | 1992-03-17 | Optical glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3238740B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4703168B2 (en) * | 2004-11-09 | 2011-06-15 | 株式会社オハラ | Optical glass |
| JP5727689B2 (en) * | 2008-03-31 | 2015-06-03 | 株式会社オハラ | Optical glass, optical element and optical instrument |
| JP2009242207A (en) * | 2008-03-31 | 2009-10-22 | Ohara Inc | Optical glass, optical element and optical device |
| JP2012126586A (en) * | 2010-12-13 | 2012-07-05 | Ohara Inc | Optical glass, preform, and optical element |
| JP6096502B2 (en) * | 2011-12-20 | 2017-03-15 | 株式会社オハラ | Optical glass and optical element |
| JP6095356B2 (en) * | 2011-12-28 | 2017-03-15 | 株式会社オハラ | Optical glass and optical element |
| JP6096501B2 (en) * | 2011-12-28 | 2017-03-15 | 株式会社オハラ | Optical glass and optical element |
| JP6553856B2 (en) * | 2013-12-27 | 2019-07-31 | 株式会社オハラ | Glass |
| CN107922242B (en) | 2015-11-30 | 2021-02-05 | 株式会社尼康 | Optical glass, optical element using optical glass, and optical device |
| TWI731991B (en) * | 2016-06-29 | 2021-07-01 | 日商小原股份有限公司 | Optical glass, preforms and optical components |
| WO2018066577A1 (en) * | 2016-10-03 | 2018-04-12 | 株式会社オハラ | Optical glass, preform, and optical element |
| JP7224099B2 (en) * | 2016-10-03 | 2023-02-17 | 株式会社オハラ | Optical glass, preforms and optical elements |
| CN106746597A (en) * | 2016-12-15 | 2017-05-31 | 成都光明光电股份有限公司 | Optical glass |
| CN109704563B (en) * | 2019-03-07 | 2021-09-21 | 湖北戈碧迦光电科技股份有限公司 | Environment-friendly lanthanide optical glass and preparation method and application thereof |
-
1992
- 1992-03-17 JP JP09175092A patent/JP3238740B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05262533A (en) | 1993-10-12 |
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