JPH06191876A - Composition for fluorophosphate optical glass - Google Patents
Composition for fluorophosphate optical glassInfo
- Publication number
- JPH06191876A JPH06191876A JP34705892A JP34705892A JPH06191876A JP H06191876 A JPH06191876 A JP H06191876A JP 34705892 A JP34705892 A JP 34705892A JP 34705892 A JP34705892 A JP 34705892A JP H06191876 A JPH06191876 A JP H06191876A
- Authority
- JP
- Japan
- Prior art keywords
- optical glass
- glass
- composition
- fluorophosphate optical
- fluorophosphate
- 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.)
- Granted
Links
- 239000005304 optical glass Substances 0.000 title claims abstract description 16
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title claims description 13
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 4
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000013022 formulation composition Substances 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 2
- 229910001632 barium fluoride Inorganic materials 0.000 abstract 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract 1
- 229910001637 strontium fluoride Inorganic materials 0.000 abstract 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 17
- 238000004031 devitrification Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- -1 SrF 2 Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000005303 fluorophosphate glass Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、弗燐酸塩光学ガラス用
調合組成物に関する。FIELD OF THE INVENTION The present invention relates to a composition for fluorophosphate optical glass.
【０００２】[0002]
【従来の技術】従来弗燐酸塩光学ガラスとしては、特公
平４−４４６１７号公報に、比較的ＡｌＦ3 、ＲＯ（２
価金属酸化物）成分が少ないものが開示され、又特開昭
６３−１４４１４１号公報に、Ａｌ2 Ｏ3 を必須成分と
するものが開示されている。2. Description of the Related Art As conventional fluorophosphate optical glass, Japanese Patent Publication No. 4-44617 discloses comparatively AlF 3 , RO (2
Those containing a small amount of (valent metal oxide) components are disclosed, and those containing Al 2 O 3 as an essential component are disclosed in JP-A-63-144141.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら特公平４
−４４６１７号公報記載のガラスの製造方法では、ＲＯ
（２価金属酸化物）成分が少なく、Ｐ2 Ｏ5 原料として
Ｈ3 ＰＯ4 やＡｌ（ＰＯ3 ）3 を用いているが、Ｈ3 Ｐ
Ｏ4 中のＨ2 Ｏによる融液中のフッ素成分の揮発増大
や、Ａｌ（ＰＯ3 ）3 の熔解性の低さより、均質なガラ
スを得ることが困難である。一方特開昭６３−１４４１
４１号公報記載のガラスの製造方法においてもＡｌ（Ｐ
Ｏ3 ）3 が使用され同様の問題がある。さらにいずれの
ガラスにおいても耐失透性が十分とは言いがたく、大量
に均質なガラスを生産することが可能なガラス組成の検
討が必要とされている。[Problems to be Solved by the Invention] However, Japanese Patent Publication No. 4
In the glass manufacturing method described in Japanese Patent Publication No.
(Divalent metal oxide) component is small, but with H 3 PO 4 and Al (PO 3) 3 as a P 2 O 5 starting material, H 3 P
It is difficult to obtain a homogeneous glass due to the increase in volatilization of the fluorine component in the melt due to H 2 O in O 4 and the low meltability of Al (PO 3 ) 3 . Meanwhile, JP-A-63-1441
Also in the glass manufacturing method described in Japanese Patent No. 41, Al (P
O 3 ) 3 is used with similar problems. Further, it cannot be said that any glass has sufficient devitrification resistance, and it is necessary to study a glass composition capable of producing a large amount of homogeneous glass.
【０００４】[0004]
【課題を解決するための手段】本発明者は上述した課題
を解決するために統計的かつ詳細な実験を行った結果、
Ｐ2 Ｏ5 成分の原料としてＢａ（ＰＯ3 ）2 を用いるこ
とにより、ガラス中にＢａＯが加わり耐失透性が向上
し、かつ熔解性が良化し、さらにＲＦ2 （２価金属弗化
物）成分の適当な比率の選定や、ＹＦ3 やＮａＦの適量
添加により耐失透性が良化し、その結果均質なガラスを
大量に製造することが可能であることを見いだした。本
発明はこのような知見に基づいてなされたもので、モル
％で Ｂａ（ＰＯ3 ）2 ２．５〜 ６．０ ＡｌＦ3 ３４．２〜４０．０ ＭｇＦ2 ４．０〜 ９．０ ＣａＦ2 ２７．０〜３４．０ ＳｒＦ2 １５．０〜２０．０ ＢａＦ2 ０．５〜 ３．４ ＹＦ3 ０．２〜 ５．０ ＮａＦ ０．２〜 ５．０ を含むことを特徴とする弗燐酸塩光学ガラス用調合組成
物を要旨とする。As a result of conducting statistical and detailed experiments to solve the above-mentioned problems, the present inventor
By using Ba (PO 3 ) 2 as the raw material of the P 2 O 5 component, BaO is added to the glass to improve the devitrification resistance and improve the meltability, and further RF 2 (divalent metal fluoride) It has been found that the devitrification resistance is improved by selecting an appropriate ratio of the components and adding an appropriate amount of YF 3 or NaF, and as a result, it is possible to mass-produce a homogeneous glass. The present invention has been made on the basis of such findings and, in mol%, Ba (PO 3 ) 2 2.5 to 6.0 AlF 3 34.2 to 40.0 MgF 2 4.0 to 9.0 CaF. 2 27.0 to 34.0 SrF 2 15.0 to 20.0 BaF 2 0.5 to 3.4 YF 3 0.2 to 5.0 NaF 0.2 to 5.0 The subject matter is a compounding composition for a fluorophosphate optical glass.
【０００５】先ず本発明における組成限定理由を述べ
る。なお、各成分の含量を示す「％」は「モル％」を示
す。Ｂａ（ＰＯ3 ）2 は、バッチ熔解性及び脱泡性がよ
く、弗燐酸塩ガラスの製造において有効な成分である。
さらに得られるガラス中に含まれるＢａＯはガラスの失
透性を抑える効果が高い。しかしながら２．５％未満で
は上記効果を得るのに不十分であり、また６．０％を超
えると分散が大きくなり目的とする光学的特性が得られ
ない。従ってＢａ（ＰＯ3 ）2 の含量は２．５〜６．０
％に限定される。First, the reasons for limiting the composition of the present invention will be described. In addition, "%" showing the content of each component shows "mol%." Ba (PO 3 ) 2 has good batch melting property and defoaming property, and is an effective component in the production of fluorophosphate glass.
Further, BaO contained in the obtained glass has a high effect of suppressing devitrification of the glass. However, if it is less than 2.5%, it is insufficient to obtain the above effect, and if it exceeds 6.0%, the dispersion becomes large and the desired optical characteristics cannot be obtained. Therefore, the content of Ba (PO 3 ) 2 is 2.5 to 6.0.
Limited to%.
【０００６】ＡｌＦ3 はガラスを安定かつ低分散にする
効果があるが、３４．２％未満では目標とする光学的特
性が得られず、４０．０％を超えると逆に失透性が強く
なる。したがってＡｌＦ3 の含量３４．２〜４０．０％
に限定される。AlF 3 has the effect of making the glass stable and low-dispersion, but if it is less than 34.2%, the desired optical properties cannot be obtained, and if it exceeds 40.0%, on the contrary, the devitrification is strong. Become. Therefore, the content of AlF 3 is 34.2 to 40.0%
Limited to
【０００７】ＭｇＦ2 、ＣａＦ2 、ＳｒＦ2 、ＢａＦ2
の各成分はガラスの耐失透性を保ち、低分散にするため
にいずれも必須の成分であり、それぞれ４．０〜９．０
％、２７．０〜３４．０％、１５．０〜２０．０％、
０．５〜３．４％の範囲外では耐失透性が悪化し安定生
産可能なガラス組成物が得られない。従ってＭｇＦ2 の
含量は４．０〜９．０％、ＣａＦ2 の含量は２７．０〜
３４．０％、ＳｒＦ2 の含量は１５．０〜２０．０％、
ＢａＦ2 の含量は０．５〜３．４％にそれぞれ限定され
る。MgF 2 , CaF 2 , SrF 2 , BaF 2
Each of the components is an essential component for maintaining the devitrification resistance of the glass and achieving a low dispersion, and each of the components is 4.0 to 9.0.
%, 27.0 to 34.0%, 15.0 to 20.0%,
When it is out of the range of 0.5 to 3.4%, the devitrification resistance is deteriorated and a glass composition which can be stably produced cannot be obtained. Therefore, the content of MgF 2 is 4.0 to 9.0% and the content of CaF 2 is 27.0.
34.0%, SrF 2 content is 15.0 to 20.0%,
The content of BaF 2 is limited to 0.5 to 3.4%, respectively.
【０００８】ＹＦ3 は少量の添加により耐失透性改善の
効果が高いが、０．２％未満ではその効果が小さく、逆
に５．０％を超えると失透性が強まる。従ってＹＦ3 の
含量は０．２〜５．０％に限定される。YF 3 has a high effect of improving devitrification resistance by adding a small amount, but if it is less than 0.2%, the effect is small, and if it exceeds 5.0%, devitrification is enhanced. Therefore, the YF 3 content is limited to 0.2 to 5.0%.
【０００９】ＮａＦは少量の添加により耐失透性を良化
する効果があるが、０．２％未満ではその効果が小さ
く、逆に５．０％を超えると屈折率が低下し、目的とす
る光学的特性が得られない。従ってＮａＦの含量は０．
２〜５．０％に限定される。さらに脱泡などの目的で少
量のＣｌ、Ｂｒ、Ｉ等の化合物を使用することは排除す
るものではない。NaF has the effect of improving the devitrification resistance by adding a small amount of it, but if it is less than 0.2%, its effect is small, and if it exceeds 5.0%, the refractive index is lowered, which is the purpose. Optical characteristics to be obtained cannot be obtained. Therefore, the content of NaF is 0.
It is limited to 2 to 5.0%. Furthermore, the use of a small amount of compounds such as Cl, Br, I for the purpose of defoaming is not excluded.
【００１０】上記の組成からなる調合組成物は、これを
常法により溶解することにより、弗燐酸塩光学ガラスを
得ることができる。本発明の調合組成物は熔解性に優れ
ており、また耐失透性を良化する効果があるため、均質
な弗燐酸塩光学ガラスを大量に製造することができる。
得られた弗燐酸塩光学ガラスは屈折率ｎd が１．４２〜
１．４４、分散率νd が９２〜９７の光学特性を有す
る。By dissolving the prepared composition having the above composition by a conventional method, a fluorophosphate optical glass can be obtained. Since the compounded composition of the present invention is excellent in melting property and has an effect of improving devitrification resistance, it is possible to mass-produce a homogeneous fluorophosphate optical glass.
The obtained fluorophosphate optical glass has a refractive index n d of 1.42 to 1.42.
It has an optical characteristic of 1.44 and a dispersion rate ν d of 92 to 97.
【００１１】[0011]
【実施例】次に本発明の実施例を説明する。表１に示す
調合組成物Ｎｏ．１〜７の各５０ｇを蓋付きの白金製坩
堝に入れ９００〜１０００℃にて熔解し、撹拌、清澄後
に鉄製型に流し込み、徐冷することにより弗燐酸塩光学
ガラスを得た。いずれの調合組成物においても、ガラス
作製時の熔解性は良好であった。得られた光学ガラスに
ついてｎd 、νd を測定し、失透テストを行なった結果
を表１に示す。なお、表１中のｎd 、νd は−３０℃／
hrでアニールした場合の値であり、又、失透テストは、
上記の方法で熔解し、撹拌清澄後、ガラスの成型温度付
近の温度（６８０℃）で２時間保持し、鉄板上に流し出
し急冷したガラス中の結晶の有無を観察した結果であ
る。EXAMPLES Examples of the present invention will be described below. Formulated composition No. 1 shown in Table 1. 50 g of each of 1 to 7 was placed in a platinum crucible with a lid, melted at 900 to 1000 ° C., stirred, clarified, poured into an iron mold, and slowly cooled to obtain a fluorophosphate optical glass. In each of the prepared compositions, the meltability during glass production was good. Table 1 shows the results of the devitrification test performed by measuring n d and ν d of the obtained optical glass. Note that n d and ν d in Table 1 are −30 ° C. /
It is the value when annealed in hr, and the devitrification test is
It is the result of observing the presence or absence of crystals in the glass melted by the above-mentioned method, stirred and clarified, held at a temperature near the glass molding temperature (680 ° C.) for 2 hours, poured onto an iron plate and rapidly cooled.
【００１２】[0012]
【表１】 表１より実施例で得られたガラスはいずれも屈折率ｎd
が１．４２〜１．４４、アッベ数νd が９２〜９７であ
り大量生産可能な耐失透性を有することが判る。[Table 1] From Table 1, all the glasses obtained in the examples have a refractive index n d.
Is 1.42 to 1.44 and the Abbe's number ν d is 92 to 97, which means that it has devitrification resistance that enables mass production.
【００１３】[0013]
【発明の効果】以上のとおり、本発明によれば、均質な
弗燐酸塩光学ガラスを大量生産するに好適な調合組成物
が提供された。As described above, according to the present invention, a formulation composition suitable for mass production of homogeneous fluorophosphate optical glass is provided.
Claims (2)
成物であって、モル％で Ｂａ（ＰＯ3 ）2 ２．５〜 ６．０ ＡｌＦ3 ３４．２〜４０．０ ＭｇＦ2 ４．０〜 ９．０ ＣａＦ2 ２７．０〜３４．０ ＳｒＦ2 １５．０〜２０．０ ＢａＦ2 ０．５〜 ３．４ ＹＦ3 ０．２〜 ５．０ ＮａＦ ０．２〜 ５．０ を含むことを特徴とする弗燐酸塩光学ガラス用調合組成
物。1. A compounding composition for melting to obtain an optical glass, which comprises, in mol%, Ba (PO 3 ) 2 2.5 to 6.0 AlF 3 34.2 to 40.0 MgF 2 4. 0 to 9.0 a CaF 2 27.0~34.0 SrF 2 15.0~20.0 BaF 2 0.5~ 3.4 YF 3 0.2~ 5.0 NaF 0.2~ 5.0 A compounding composition for a fluorophosphate optical glass, which comprises:
合組成物を溶解して得られ、屈折率ｎd が１．４２〜
１．４４、分散率νd が９２〜９７の光学的特性を有す
ることを特徴とする弗燐酸塩光学ガラス。2. A solution obtained by dissolving the formulation composition for a fluorophosphate optical glass according to claim 1, and having a refractive index n d of 1.42.
1. A fluorophosphate optical glass having an optical property of 1.44 and a dispersion ratio ν d of 92 to 97.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34705892A JP3194804B2 (en) | 1992-12-25 | 1992-12-25 | Preparation composition for fluorophosphate optical glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34705892A JP3194804B2 (en) | 1992-12-25 | 1992-12-25 | Preparation composition for fluorophosphate optical glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06191876A true JPH06191876A (en) | 1994-07-12 |
| JP3194804B2 JP3194804B2 (en) | 2001-08-06 |
Family
ID=18387637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34705892A Expired - Lifetime JP3194804B2 (en) | 1992-12-25 | 1992-12-25 | Preparation composition for fluorophosphate optical glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3194804B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0948633A (en) * | 1995-08-02 | 1997-02-18 | Nikon Corp | Optical glass for polarizing optical system and polarizing beam splitter using the same |
| JP2005272253A (en) * | 2004-03-26 | 2005-10-06 | Hoya Corp | Glass outflow nozzle, method for producing glass article, and method for producing optical element |
| 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 |
| US7974020B2 (en) | 2006-09-28 | 2011-07-05 | Hoya Corporation | Lens and process for the production thereof |
| WO2019142397A1 (en) * | 2018-01-18 | 2019-07-25 | 株式会社ニコン | Optical glass, optical element equipped with optical glass, and optical device |
| CN116143408A (en) * | 2023-02-13 | 2023-05-23 | 中国科学院西安光学精密机械研究所 | Low nonlinear fluorophosphate UV window glass |
-
1992
- 1992-12-25 JP JP34705892A patent/JP3194804B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0948633A (en) * | 1995-08-02 | 1997-02-18 | Nikon Corp | Optical glass for polarizing optical system and polarizing beam splitter using the same |
| JP2005272253A (en) * | 2004-03-26 | 2005-10-06 | Hoya Corp | Glass outflow nozzle, method for producing glass article, and method for producing optical element |
| US7974020B2 (en) | 2006-09-28 | 2011-07-05 | Hoya Corporation | Lens and process for the production 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 |
| WO2019142397A1 (en) * | 2018-01-18 | 2019-07-25 | 株式会社ニコン | Optical glass, optical element equipped with optical glass, and optical device |
| CN116143408A (en) * | 2023-02-13 | 2023-05-23 | 中国科学院西安光学精密机械研究所 | Low nonlinear fluorophosphate UV window glass |
| CN116143408B (en) * | 2023-02-13 | 2024-09-17 | 中国科学院西安光学精密机械研究所 | Low non-linear fluorophosphate ultraviolet window glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3194804B2 (en) | 2001-08-06 |
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