JP4035898B2 - Optical glass for press-molded lenses - Google Patents
Optical glass for press-molded lenses Download PDFInfo
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- JP4035898B2 JP4035898B2 JP23535998A JP23535998A JP4035898B2 JP 4035898 B2 JP4035898 B2 JP 4035898B2 JP 23535998 A JP23535998 A JP 23535998A JP 23535998 A JP23535998 A JP 23535998A JP 4035898 B2 JP4035898 B2 JP 4035898B2
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- 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
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
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Description
【０００１】
【産業上の利用分野】
本発明は比較的低温でプリフォームの熱間成形が可能で、かつプレス成形レンズに適した光学ガラスに関する。
【０００２】
【従来の技術】
精密光学部品として、例えばレンズをプレス成形により製造する方式は近年広く使用されている。プレス成形は、それぞれ相対向する面が転写面となった下型及び上型を胴型内に設けるようにした成形型を用い、この成形型の下型と上型との間にガラス素材を配置した状態で加熱炉内に搬入して、この加熱炉内でガラス素材をプレス成形が可能な屈伏温度にまで加熱した上で、上下の型に加圧力を作用させてプレス成形することにより、ガラス素材に下型及び上型の転写面形状を転写するものである。プレス成形に用いられるガラス素材としては、レンズ形状にできるだけ近似した形状のプリフォームが用いられる。このプリフォームは熱間成形により形成され、ガラスを溶融状態にまで加熱してその溶融ガラスを所定量だけ型に受けることにより生成される。
【０００３】
以上のことから、プレス成形に用いられるガラスの特性としては、まずプレス成形が可能な温度、つまり屈伏温度ができるだけ低いものを用いるのが望ましい。また、プリフォームを熱間成形するに当っては、ガラスの粘度が高い方が精度良く成形できることになる。従って、プレス成形に適したガラスとしては、屈伏温度（Ｔｓ）及び液相温度（Ｌ．Ｔ．）ができるだけ低いものが望まれる。
【０００４】
ここで、屈折率（ｎｄ）が１．５２〜１．６２、アッベ数（νｄ）が５９．０〜６４．０の範囲の光学恒数を持つプレス成形レンズ用ガラスとして、Ｐ2Ｏ5−ＺｎＯ−Ｌｉ2Ｏ系ガラス（特許２６１６９８０号公報）が知られている。この公知のガラスは屈伏温度が５００℃以下というように低いことから、プレス成形レンズ用のプリフォームとしては優れた特性を有している。
【０００５】
【発明が解決しようとする課題】
ところで、前述した公知のガラスの組成には、屈伏温度を下げるためにＺｎＯを多量に含んでいる関係から、液相温度の上昇を招き、プリフォームの熱間成形時の精度が劣るという欠点がある。また、光ファイバー用のガラスとして、Ｐ2Ｏ5−ＺｎＯ−Ｌｉ2Ｏ系ガラスを用いることが、特公平４−３２０１５号公報に示されている。このガラスの組成としては、希土類酸化物を用いることにより屈折率を高くし、かつ転移点温度を下げるようにしている。ただし、希土類酸化物としてＬａ2Ｏ3 を用いていることから、レンズとして十分に耐失透性の良いガラスは得られていない。
【０００６】
従って、本発明の目的は、 屈折率（ｎｄ）が１．５６〜１．６２で、アッベ数（νｄ）が５６．０〜６４．０の範囲の光学恒数を有し、しかもプレス成形レンズに適した低い屈伏温度を維持しつつ、 比較的低温でプリフォームの熱間成形が可能な光学ガラスを提供することにある。
【０００７】
【課題を解決するための手段】
本発明者等は以上のような従来技術の欠点を解消すべく鋭意研究を行った結果、希土類酸化物としてＬａ2Ｏ3 の代わりにＧｄ2Ｏ3 を加えたＰ2Ｏ5−ＺｎＯ−Ｌｉ2Ｏ−Ｇｄ2Ｏ3 系が、低い屈伏温度を維持しつつ液相温度を著しく下げることを知見したことによって発明を完成するに至った。
【０００８】
而して、本発明によるガラスの組成を重量％で表すと、
Ｐ2Ｏ5 ４８〜５８％
Ａｌ2Ｏ3 １〜 ３％
Ｌｉ2Ｏ １〜 ４％
Ｎａ2Ｏ ０〜 ４％
ＭｇＯ ０〜 ５％
ＣａＯ ０〜１０％
ＳｒＯ ０〜１０％
ＢａＯ ２〜１５％
ただし、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合量 ８〜２０％
ＺｎＯ １８〜３２％
Ｇｄ2Ｏ3 １〜 ５％
ＺｒＯ2 ０〜 １％
Ｎｂ2Ｏ5 ０〜 ２％
である。
【０００９】
本発明の光学ガラスの組成における各成分範囲を以上のように検定した理由は次の通りである。
【００１０】
まず、Ｐ2Ｏ5 はガラスの骨格を構成する主成分であるが、 本願の目的とする光学恒数、つまり屈折率（ｎｄ）１．５６〜１．６２、アッベ数（νｄ）５６．０〜６４．０の範囲の光学恒数を得るために、このＰ2Ｏ5 の含量は４８％ 〜５８％に限定される。
【００１１】
Ａｌ2Ｏ3 は１％以上添加することにより液相温度を下げ、耐候性を向上させる。しかし３％を超えると逆に液相温度を上昇させる。
【００１２】
Ｌｉ2Ｏは屈伏温度の低温度化に必要な成分で１％以上必要である。ただし、添加量が４％を超えると液相温度の上昇を招くことになる。
【００１３】
Ｎａ2Ｏを少量添加すると、屈伏温度と液相温度を改善する上で有効である。ただし、４％を超えると液相温度が逆に上昇するとともに耐候性が悪化する。
【００１４】
ＢａＯはアッベ数を高く保持し液相温度の低いガラスを得るのに必須であり、少なくとも２％以上必要だが、添加量が１５％を超えると屈伏温度が上昇するので望ましくはない。
【００１５】
ＭｇＯ，ＣａＯ，ＳｒＯは液相温度の改善と光学恒数の調整を行う上で有効である。ただし、それらが各々５％，１０％，１５％を超えると液相温度が上がってしまう。また、所望の屈伏温度と液相温度を得るということから、ＭｇＯ，ＣａＯ，ＳｒＯ，ＢａＯの合量は８〜２０％に限定される。
【００１６】
ＺｎＯは屈伏温度が低くかつ屈折率が比較的高いガラスを得るのに有効な成分であり１８％以上必要だが、３２％を超えると液相温度が上昇するとともに所望のアッベ数を得るのが困難になる。
【００１７】
Ｇｄ2Ｏ3は既に説明したように、液相温度を下げるのに有効であり、かつ耐候性改善の効果もあり、１％以上必要である。ただし、Ｇｄ2Ｏ3 の添加量が５％を超えると逆に液相温度が上昇する。
【００１８】
ＺｒＯ2 ，Ｎｂ2Ｏ5 は耐候性を改善する効果が大きいので、必要に応じて微量添加される。ただし、ＺｒＯ2 が１％を超えると液相温度が上昇し、Ｎｂ2Ｏ5が２％を超えると所望のアッベ数を維持できなくなる。
【００１９】
【実施例】
次に本発明に係る実施組成例および前記従来の光学ガラスの比較組成例を、屈折率（ｎｄ）、アッベ数（νｄ）、屈状温度（Ｔｓ）、液相温度（Ｌ．Ｔ．）の測定結果とともに表１，２に示す。表２の比較例Ｎｏ．７は表１の実施例Ｎｏ．１のＧｄ2Ｏ3 をＬａ2Ｏ3 に置き換えた組成であり、比較例Ｎｏ．８は実施例Ｎｏ．５のＧｄ2Ｏ3 をＬａ2Ｏ3 に置き換えた組成である。
【００２０】
表記の光学ガラスは、Ｐ2Ｏ5 原料として正燐酸またはメタ燐酸塩を用い、他の成分についてはメタ燐酸塩、炭酸塩、硝酸塩、酸化物等を用い、 これらの原料を所定の割合に調合して白金製るつぼに投入し、１０００〜１２００℃の電気炉にて溶融、 攪拌均質化してから鉄製型に流し込み徐冷することにより得る。
【００２１】
表中の屈折率（ｎｄ）、アッベ数（νｄ）は、速度−１０Ｋ／ｈｏｕｒにて徐冷した場合の結果である。屈状温度（Ｔｓ）は熱膨張測定機を用いて５Ｋ／ｍｉｎで昇温した場合の結果である。また、液相温度（Ｌ．Ｔ．）は５００〜１０００℃の温度勾配のついた失透試験装置に３０分保持した後、倍率１００倍の偏光顕微鏡で結晶の有無を観察して得た結果である。
【００２２】
【表１】
【表２】
【００２４】
【発明の効果】
本発明のＰ2Ｏ5−ＺｎＯ−Ｌｉ2Ｏ−Ｇｄ2Ｏ3 系光学ガラスは、屈折率（ｎｄ）１．５６〜１．６２、アッベ数（νｄ）５６．０〜６４．０の範囲の光学恒数の範囲の光学恒数を有し、しかもプレス成形レンズに適した４４０℃以下の屈状温度（Ｔｓ）を維持しつつ、８７０℃以下の液相温度（Ｌ．Ｔ．）を有しているため、比較的低い温度でプリフォームの熱間成形を行うことができる等といった効果を奏する。[0001]
[Industrial application fields]
The present invention relates to an optical glass capable of hot forming a preform at a relatively low temperature and suitable for a press-molded lens.
[0002]
[Prior art]
As a precision optical component, for example, a method of manufacturing a lens by press molding has been widely used in recent years. Press molding uses a molding die in which a lower die and an upper die each having a surface facing each other as a transfer surface are provided in a body die, and a glass material is placed between the lower die and the upper die. By carrying it into the heating furnace in the state of being placed and heating the glass material to a yield temperature where press molding is possible in this heating furnace, by applying pressure to the upper and lower molds and press molding, The transfer surface shape of the lower mold and the upper mold is transferred to a glass material. As a glass material used for press molding, a preform having a shape as close as possible to the lens shape is used. This preform is formed by hot forming, and is produced by heating the glass to a molten state and receiving the molten glass in a predetermined amount.
[0003]
From the above, it is desirable that the glass used for press molding should have a temperature at which press molding can be performed, that is, a material having the lowest yield temperature. In addition, when the preform is hot-formed, the glass having a higher viscosity can be formed with higher accuracy. Therefore, a glass suitable for press molding is desired to have as low a yield temperature (Ts) and a liquidus temperature (LT) as possible.
[0004]
Here, as a glass for press-molded lenses having an optical constant having a refractive index (nd) of 1.52 to 1.62 and an Abbe number (νd) of 59.0 to 64.0, P 2 O 5 − ZnO—Li 2 O-based glass (Japanese Patent No. 2616980) is known. This known glass has an excellent characteristic as a preform for a press-molded lens because the deformation temperature is as low as 500 ° C. or less.
[0005]
[Problems to be solved by the invention]
By the way, the above-mentioned known glass composition has a drawback in that since it contains a large amount of ZnO in order to lower the yield temperature, the liquidus temperature rises and the accuracy during hot forming of the preform is inferior. is there. Japanese Patent Publication No. 4-32015 discloses the use of P 2 O 5 —ZnO—Li 2 O-based glass as glass for optical fibers. As the composition of this glass, a rare earth oxide is used to increase the refractive index and lower the transition temperature. However, since La 2 O 3 is used as a rare earth oxide, a glass having sufficiently good devitrification resistance as a lens has not been obtained.
[0006]
Accordingly, an object of the present invention is to provide an optical constant having a refractive index (nd) of 1.56 to 1.62, an Abbe number (νd) of 56.0 to 64.0, and a press-molded lens. It is an object of the present invention to provide an optical glass capable of hot forming a preform at a relatively low temperature while maintaining a low deformation temperature suitable for the above.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to eliminate the drawbacks of the prior art as described above, the present inventors have found that P 2 O 5 —ZnO—Li in which Gd 2 O 3 is added instead of La 2 O 3 as a rare earth oxide. The inventors have found that the 2 O—Gd 2 O 3 system significantly lowers the liquidus temperature while maintaining a low yielding temperature, thereby completing the invention.
[0008]
Thus, when the composition of the glass according to the present invention is expressed in weight%,
P 2 O 5 48~58%
Al 2 O 3 1-3%
Li 2 O 1-4%
Na 2 O 0-4%
MgO 0-5%
CaO 0-10%
SrO 0-10%
BaO 2-15%
However, the total amount of MgO + CaO + SrO + BaO 8-20%
ZnO 18-32%
Gd 2 O 3 1-5%
ZrO 2 0 to 1%
Nb 2 O 5 0-2%
It is.
[0009]
The reason why each component range in the composition of the optical glass of the present invention was tested as described above is as follows.
[0010]
First, P 2 O 5 is a main component constituting the skeleton of the glass, but the optical constants of the present application, that is, refractive index (nd) 1.56-1.62, Abbe number (νd) 56.0. In order to obtain an optical constant in the range of ˜64.0, the content of P 2 O 5 is limited to 48% to 58%.
[0011]
Al 2 O 3 is added at 1% or more to lower the liquidus temperature and improve the weather resistance. However, if it exceeds 3%, the liquidus temperature is raised.
[0012]
Li 2 O is a component necessary for lowering the yield temperature, and 1% or more is necessary. However, when the addition amount exceeds 4%, the liquidus temperature is increased.
[0013]
Addition of a small amount of Na 2 O is effective in improving the yield temperature and liquidus temperature. However, if it exceeds 4%, the liquidus temperature rises conversely and the weather resistance deteriorates.
[0014]
BaO is essential for obtaining a glass having a high Abbe number and a low liquidus temperature, and is required to be at least 2% or more. However, if the added amount exceeds 15%, the deformation temperature is undesirably increased.
[0015]
MgO, CaO, and SrO are effective in improving the liquid phase temperature and adjusting the optical constant. However, if they exceed 5%, 10%, and 15%, respectively, the liquidus temperature rises. Moreover, since the desired yield temperature and liquidus temperature are obtained, the total amount of MgO, CaO, SrO, and BaO is limited to 8 to 20%.
[0016]
ZnO is an effective component for obtaining a glass having a low yield temperature and a relatively high refractive index, and is required to be 18% or more. However, if it exceeds 32%, the liquidus temperature rises and it is difficult to obtain a desired Abbe number. become.
[0017]
As already described, Gd 2 O 3 is effective for lowering the liquidus temperature, and also has an effect of improving weather resistance, and needs to be 1% or more. However, when the amount of Gd 2 O 3 added exceeds 5%, the liquidus temperature increases.
[0018]
ZrO 2 and Nb 2 O 5 have a great effect of improving the weather resistance, and are added in small amounts as necessary. However, if ZrO 2 exceeds 1%, the liquidus temperature rises, and if Nb 2 O 5 exceeds 2%, the desired Abbe number cannot be maintained.
[0019]
【Example】
Next, an example composition according to the present invention and a comparative composition example of the above-described conventional optical glass have a refractive index (nd), Abbe number (νd), bent temperature (Ts), and liquidus temperature (LT). It shows in Table 1, 2 with a measurement result. Comparative Example No. 2 in Table 2 7 is an example No. 7 in Table 1. No. 1 Gd 2 O 3 is replaced with La 2 O 3 . 8 shows Example No. No. 5 Gd 2 O 3 is replaced with La 2 O 3 .
[0020]
The optical glass indicated uses orthophosphoric acid or metaphosphate as the P 2 O 5 raw material, and metaphosphorate, carbonate, nitrate, oxide, etc. are used for the other components, and these raw materials are prepared in a predetermined ratio. Then, it is put into a platinum crucible, melted in a 1000 to 1200 ° C. electric furnace, homogenized with stirring, poured into an iron mold and gradually cooled.
[0021]
The refractive index (nd) and Abbe number (νd) in the table are the results when cooling slowly at a speed of −10 K / hour. The bent temperature (Ts) is the result when the temperature is increased at 5 K / min using a thermal expansion measuring machine. The liquidus temperature (LT) was obtained by observing the presence or absence of crystals with a polarizing microscope at a magnification of 100 times after being held in a devitrification test apparatus with a temperature gradient of 500 to 1000 ° C. for 30 minutes. It is.
[0022]
[Table 1]
[Table 2]
[0024]
【The invention's effect】
The P 2 O 5 —ZnO—Li 2 O—Gd 2 O 3 optical glass of the present invention has a refractive index (nd) of 1.56 to 1.62 and an Abbe number (νd) of 56.0 to 64.0. The liquid phase temperature (LT) of 870 ° C. or lower is maintained while maintaining the bending temperature (Ts) of 440 ° C. or lower, which is suitable for a press-molded lens. Since it has, there exists an effect that a preform can be hot formed at a relatively low temperature.
Claims (1)
Ｐ2Ｏ5 ４８〜５８％
Ａｌ2Ｏ3 １〜 ３％
Ｌｉ2Ｏ １〜 ４％
Ｎａ2Ｏ ０〜 ４％
ＭｇＯ ０〜 ５％
ＣａＯ ０〜１０％
ＳｒＯ ０〜１０％
ＢａＯ ２〜１５％
ただし、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合量 ８〜２０％
ＺｎＯ １８〜３２％
Ｇｄ2Ｏ3 １〜 ５％
ＺｒＯ2 ０〜 １％
Ｎｂ2Ｏ5 ０〜 ２％
からなり、屈伏温度（Ｔｓ）が４４０℃以下、液相温度（Ｌ．Ｔ．）が８７０℃以下で、屈折率（ｎｄ）が１．５６〜１．６２、アッベ数（νｄ）が５６．０〜６４．０である光学ガラス。% By weight P 2 O 5 48-58%
Al 2 O 3 1-3%
Li 2 O 1-4%
Na 2 O 0-4%
MgO 0-5%
CaO 0-10%
SrO 0-10%
BaO 2-15%
However, the total amount of MgO + CaO + SrO + BaO 8-20%
ZnO 18-32%
Gd 2 O 3 1-5%
ZrO 2 0 to 1%
Nb 2 O 5 0-2%
The yield temperature (Ts) is 440 ° C. or lower, the liquidus temperature (LT) is 870 ° C. or lower, the refractive index (nd) is 1.56 to 1.62, and the Abbe number (νd) is 56. Optical glass that is 0-64.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23535998A JP4035898B2 (en) | 1998-08-21 | 1998-08-21 | Optical glass for press-molded lenses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23535998A JP4035898B2 (en) | 1998-08-21 | 1998-08-21 | Optical glass for press-molded lenses |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000072474A JP2000072474A (en) | 2000-03-07 |
| JP4035898B2 true JP4035898B2 (en) | 2008-01-23 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23535998A Expired - Fee Related JP4035898B2 (en) | 1998-08-21 | 1998-08-21 | Optical glass for press-molded lenses |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4035898B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10239572B3 (en) * | 2002-08-23 | 2004-01-08 | Schott Glas | Lead-free and preferably arsenic-free optical heavy crown glasses and their use |
| JP2004168593A (en) * | 2002-11-20 | 2004-06-17 | Minolta Co Ltd | Optical glass |
| US7157391B2 (en) * | 2002-12-27 | 2007-01-02 | Hoya Corporation | Optical glass, preform for press molding and optical element |
| JP4162532B2 (en) * | 2003-04-18 | 2008-10-08 | Ｈｏｙａ株式会社 | Optical glass, press-molding preform and manufacturing method thereof, optical element and manufacturing method thereof |
| JP4442168B2 (en) * | 2003-09-10 | 2010-03-31 | コニカミノルタオプト株式会社 | Optical glass and optical element |
| JP6540706B2 (en) | 2014-09-05 | 2019-07-10 | 株式会社ニコン | Optical glass, optical element using optical glass, optical device |
| CN114853338A (en) * | 2017-06-20 | 2022-08-05 | 成都光明光电有限责任公司 | Low melting point glass |
-
1998
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