JP3883547B2 - Glass composition - Google Patents
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- JP3883547B2 JP3883547B2 JP2004085450A JP2004085450A JP3883547B2 JP 3883547 B2 JP3883547 B2 JP 3883547B2 JP 2004085450 A JP2004085450 A JP 2004085450A JP 2004085450 A JP2004085450 A JP 2004085450A JP 3883547 B2 JP3883547 B2 JP 3883547B2
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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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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Description
本発明は環境に有害なあるいはその恐れのあるＰｂＯ，ＣｄＯ及びＢａＯや、高価なＧｅＯ2及びＴａ2Ｏ5を含まず、ＳｉＯ2，Ｂ2Ｏ3，Ｌａ2Ｏ3，Ｇｄ2Ｏ3，Ｎｂ2Ｏ5，ＴｉＯ2，ＺｎＯ，Ｌｉ2Ｏ，Ｎａ2Ｏを必須成分とする屈折率（ｎｄ）１．７〜１．８，アッベ数（νｄ）４４〜４６の光学定数を有するモールドプレス用光学ガラス、さらに云えば、ガラス融体から直接モールドプレス用ガラスのプリフォームの成形に適する光学ガラス組成物に関する。 The present invention does not include PbO, CdO and BaO which are harmful to the environment or may be expensive, and expensive GeO 2 and Ta 2 O 5, and include SiO 2 , B 2 O 3 , La 2 O 3 , Gd 2 O 3 , Mold press having an optical constant of refractive index (nd) 1.7 to 1.8 and Abbe number (νd) 44 to 46, which contains Nb 2 O 5 , TiO 2 , ZnO, Li 2 O, and Na 2 O as essential components. More particularly, the present invention relates to an optical glass composition suitable for molding a mold press glass preform directly from a glass melt.
最近、所望する光学素子（レンズ）の短焦点化や小曲率化、また機器の小型化や低価格化に対応するための光学素子材料が強く求められている。これらの材料は直接モールドプレスにより成形されることが多い。モールドプレス用光学ガラスの組成は、これまでにも以下列挙する、例えば、特許文献１乃至１０に開示されている。 In recent years, there has been a strong demand for optical element materials for shortening the focal length and reducing the curvature of a desired optical element (lens), as well as reducing the size and cost of equipment. These materials are often formed directly by a mold press. The composition of the optical glass for mold press is disclosed in, for example, Patent Documents 1 to 10 listed below.
しかしながら、上記文献等で開示されているガラスの組成は、本発明で目標とする光学定数を有しながら、ガラス融体から直接所望する形状のプリフォームを成形する技術において必要とするガラス融体の失透に対する十分な安定性を有すること、溶融中揮発等に起因する光学定数の変動が少ないこと、環境に有害な成分を含有しないこと、高価格の原料を使用しないことなど、の観点に照らし合わせてみると、必ずしも満足すべきものでなかった。 However, the glass composition disclosed in the above documents has the glass melt required in the technique of directly forming a preform having a desired shape directly from the glass melt while having the optical constant targeted by the present invention. From the viewpoints of having sufficient stability against devitrification, low fluctuations in optical constants due to volatilization during melting, not containing environmentally harmful components, and not using expensive raw materials. In comparison, it was not always satisfactory.
本発明の第１の特徴構成は、そのような問題点を解決するために鋭意研究した結果なされたものであり、質量％で、ＳｉＯ2 ８〜１３％，Ｂ2Ｏ3 １６〜２１％，Ｌａ2Ｏ3 ３２〜３７％，Ｇｄ2Ｏ3 １３．５〜１６．５％，Ｎｂ2Ｏ5 ２〜４．５％，ＴｉＯ2 １〜３％，ＺｎＯ ８〜１１．５％，Ｌｉ2Ｏ ２〜４％，Ｎａ2Ｏ １〜４％を含むガラス組成物である。 The first characteristic configuration of the present invention has been made as a result of intensive studies to solve such problems, and in terms of mass%, SiO 2 8 to 13%, B 2 O 3 16 to 21%, La 2 O 3 32 to 37%, Gd 2 O 3 13.5 to 16.5%, Nb 2 O 5 2 to 4.5%, TiO 2 1 to 3%, ZnO 8 to 11.5%, Li 2 It is a glass composition containing O 2-4% and Na 2 O 1-4%.
また、本発明の第２の特徴構成は、上記ガラス組成物に、さらに質量％で、ＺｒＯ2 ０〜１．５％，Ａｌ2Ｏ3 ０〜１．５％，Ｙ2Ｏ3 ０〜１．５％，ＣａＯ ０〜２％，ＳｒＯ ０〜２％，Ｋ2Ｏ ０〜２％を、合計で５質量％以下含ませたガラス組成物である。 The second characteristic feature of the present invention, the above glass composition, in addition mass%, ZrO 2 0~1.5%, Al 2 O 3 0~1.5%, Y 2 O 3 0~1 .5%, CaO 0-2%, SrO 0-2%, K 2 O 0-2% in total, 5% by mass or less in total.
さらに、本発明の第３の特徴構成は、屈折率（ｎｄ）１.７〜１.８，アッベ数（νｄ）４４〜４６の光学定数を有するガラス組成物で解決を図るものである。 Furthermore, the third characteristic configuration of the present invention is to solve the problem with a glass composition having optical constants of refractive index (nd) 1.7 to 1.8 and Abbe number (νd) 44 to 46.
つまり、目標とする光学定数を有するガラスを得るためには、ガラス形成酸化物としてＢ2Ｏ3、主として高屈折率を与える成分としてＬａ2Ｏ3、主としてガラスの溶解性を良好にする成分としてＲＯ（Ｒは２価金属元素、Ｏは酸素）からなるＢ2Ｏ3−Ｌａ2Ｏ3−ＲＯを基本系とし、目標とするガラスに向かって成分及び含有量を調整するのが一つの方法である。この系を基に使用可能成分の制約を考慮しながら、光学定数を損ねずガラスの安定性を図ったのが本発明のＢ2Ｏ3−ＳｉＯ2−Ｌａ2Ｏ3−Ｇｄ2Ｏ3−Ｎｂ2Ｏ5−ＴｉＯ2−Ｌｉ2Ｏ−Ｎａ2Ｏ系ガラスである。個々の成分の好適含有量は、光学定数への影響と、主として、ガラスの失透に対する安定性に与える影響との兼ね合いで決定した。失透に対する安定性は、主として、液相温度（ガラスから析出する結晶が存在し得る最高温度）と液相温度付近のガラス融液の粘性によって支配され、一般に液相温度が低いほど、また粘性が大きいほどガラスは安定で、ガラス融体からのプリフォームの直接成形に適する。 That is, in order to obtain a glass having a target optical constant, B 2 O 3 as a glass-forming oxide, La 2 O 3 as a component that mainly gives a high refractive index, and as a component that mainly improves the solubility of the glass. One method is to use B 2 O 3 —La 2 O 3 —RO composed of RO (R is a divalent metal element and O is oxygen) as a basic system and adjust the components and content toward the target glass. It is. The B 2 O 3 —SiO 2 —La 2 O 3 —Gd 2 O 3 — of the present invention was designed to stabilize the glass without impairing the optical constants while taking into account the restrictions on the components that can be used based on this system. Nb 2 O 5 —TiO 2 —Li 2 O—Na 2 O-based glass. The preferred content of each component was determined by a balance between the influence on the optical constant and the influence on the stability against devitrification of the glass. The stability against devitrification is mainly governed by the liquidus temperature (the maximum temperature at which crystals precipitated from the glass can exist) and the viscosity of the glass melt near the liquidus temperature. Generally, the lower the liquidus temperature, the more viscous The larger the is, the more stable the glass is and it is suitable for direct molding of a preform from a glass melt.
次に個々の成分の作用効果について記す。
Ｂ2Ｏ3とＳｉＯ2はガラス形成成分であるが、Ｌａ2Ｏ3を多量に含む高屈折率系ではＢ2Ｏ3が主体となる。一般にガラス形成成分が多いほどガラスは失透に対して安定であるが、この系では、多すぎると所望の屈折率が得られないばかりか溶解中にＢ2Ｏ3成分の揮発による組成変動のほか、ガラス融液が均一相にならないという現象（不混和）が起こる。Ｂ2Ｏ3の一部をＳｉＯ2で置換していくと、少量の置換の場合にはガラス網目の強化及びガラス融液の粘性の増加により失透の防止に効果がある。しかし置換量がある限度を越すと、融液の不混和やＢ2Ｏ3成分の揮発増加に導く恐れがある。目標屈折率を得るための多量の高屈折成分の存在下では、Ｂ2Ｏ3 １６〜２１質量％、ＳｉＯ2 ８〜１３質量％が好適である。
Next, the effect of each component will be described.
B 2 O 3 and SiO 2 are glass forming components, but B 2 O 3 is mainly used in a high refractive index system containing a large amount of La 2 O 3 . Generally Glass more glass-forming components are often are stable to devitrification, in this system, too much, during the dissolution not only desired refractive index is not obtained B 2 O 3 component volatilized due to compositional variation of In addition, a phenomenon (immiscibility) that the glass melt does not become a homogeneous phase occurs. When a part of B 2 O 3 is replaced with SiO 2 , in the case of a small amount of replacement, there is an effect of preventing devitrification by strengthening the glass network and increasing the viscosity of the glass melt. However, if the substitution amount exceeds a certain limit, it may lead to immiscibility of the melt and increased volatilization of the B 2 O 3 component. In the presence of a large amount of high refractive component for obtaining the target refractive index, B 2 O 3 16-21% by mass and SiO 2 8-13% by mass are suitable.
Ｌａ2Ｏ3，Ｇｄ2Ｏ3，Ｎｂ2Ｏ5などは、主として高屈折率を与える成分である。ガラスの高屈折率化だけならば、Ｌａ2Ｏ3単独の使用でも達せられるが、その一部をＧｄ2Ｏ3とＮｂ2Ｏ5で置換したほうが、他の成分の量が同じならば、ガラスは失透に対してより安定になる。所望の屈折率を得るためには３成分合計でほぼ５０質量％，あるいはそれ以上が必要である。光学定数に与える効果及び原料価格を考慮すると、Ｇｄ2Ｏ3はＬａ2Ｏ3より少なく、Ｎｂ2Ｏ5はさらに少なくしたほうがよい。このような観点から、Ｌａ2Ｏ3は３２〜３７質量％，Ｇｄ2Ｏ3 １３．５〜１６．５質量％，Ｎｂ2Ｏ5 ２〜４．５質量％が好適範囲と決定した。 La 2 O 3 , Gd 2 O 3 , Nb 2 O 5 and the like are components that mainly give a high refractive index. If only the refractive index of the glass is increased, the use of La 2 O 3 alone can be achieved. However, if a part of the glass is replaced with Gd 2 O 3 and Nb 2 O 5 in the same amount of other components, Glass becomes more stable against devitrification. In order to obtain a desired refractive index, the total of the three components requires approximately 50% by mass or more. Considering the effect on the optical constant and the raw material price, it is preferable that Gd 2 O 3 is less than La 2 O 3 and Nb 2 O 5 is further reduced. From such a viewpoint, it was determined that La 2 O 3 was in a preferred range of 32 to 37% by mass, Gd 2 O 3 13.5 to 16.5% by mass, and Nb 2 O 5 2 to 4.5% by mass.
環境への配慮から、ＰｂＯ，ＣｄＯ，ＢａＯを使用しないという条件下で、ＲＯ成分の代表として採用したのがＺｎＯである。この成分は、主として、ガラスの溶解性に関係し、少なすぎると原料の均一溶融を阻害したり、融液の不混和を惹き起こす危険性がある。そのためＺｎＯの含有量は多いほうがガラスの溶解性や融液の安定性にとって好ましいが、含有量を増やしすぎると光学定数に与える影響が大きくなる。そのためＺｎＯの含有量を比較的低く抑え、不足分をＬｉ2ＯとＮａ2Ｏで補うことにした。少量のＬｉ2ＯとＮａ2Ｏの導入はガラスの溶解性及び融液の均一化を改善するのに効果的であり、失透防止の点からも望ましく、両者を共存させたほうがより効果的である。しかし含有量が多すぎると、逆に失透を起こしやすくし、また屈折率を低下させる。この微妙なバランスの上で、ＺｎＯについては８〜１１．５質量％，Ｌｉ2Ｏについては２〜４質量％，Ｎａ2Ｏについは１〜４質量％が好適と決定した。 In consideration of the environment, ZnO is adopted as a representative RO component under the condition that PbO, CdO, and BaO are not used. This component is mainly related to the solubility of the glass, and if it is too small, there is a risk of inhibiting the uniform melting of the raw material or causing the melt to be immiscible. Therefore, a higher ZnO content is preferable for glass solubility and melt stability, but if the content is excessively increased, the influence on the optical constant is increased. Therefore, the content of ZnO was kept relatively low, and the shortage was made up with Li 2 O and Na 2 O. The introduction of a small amount of Li 2 O and Na 2 O is effective in improving the glass meltability and the homogenization of the melt, which is desirable from the viewpoint of preventing devitrification, and it is more effective to coexist both. It is. However, when the content is too large, devitrification tends to occur, and the refractive index is lowered. Based on this delicate balance, it was determined that 8 to 11.5% by mass for ZnO, 2 to 4% by mass for Li 2 O, and 1 to 4% by mass for Na 2 O were preferable.
ＴｉＯ2はガラスの高屈折率化に非常に有効な成分であるが、一方アッベ数を小さくする効果も大きい。またＴｉＯ2は、多くの結晶化ガラス生成系（その多くは、ＳｉＯ2−Ａｌ2Ｏ3−Ｌｉ2Ｏ系）において結晶核形成剤として用いられることから、失透を助長する成分のように考えられがちであるが、本発明ガラスの成分系においては、少量の添加は液相温度を低下させ、ガラスの失透防止に寄与する。導入量は３％が限度であり、１〜３質量％が好適である。 TiO 2 is a very effective component for increasing the refractive index of glass, but has a great effect of reducing the Abbe number. In addition, TiO 2 is used as a crystal nucleating agent in many crystallized glass production systems (most of which are SiO 2 —Al 2 O 3 —Li 2 O systems). Although it tends to be considered, in the component system of the glass of the present invention, addition of a small amount reduces the liquidus temperature and contributes to prevention of devitrification of the glass. The introduction amount is limited to 3%, and preferably 1 to 3% by mass.
本発明の第２特徴構成成分は、その少量の導入により液相温度の低下、成分によっては融液の粘性の増加を通じて、いずれも失透に対して安定に寄与する成分である。しかし、導入量が多すぎると、所望の光学定数を逸脱させるなどの恐れがあるので、ＺｒＯ2，Ａｌ2Ｏ3，Ｙ2Ｏ3については、それぞれ０〜１．５質量％，ＣａＯ，ＳｒＯ，Ｋ2Ｏについては、それぞれ０〜２質量％の範囲に留め、その合計量も５質量％以下に留めるのが適当である。 The second characteristic component of the present invention is a component that contributes stably to devitrification through a decrease in the liquid phase temperature by introduction of a small amount thereof, and an increase in the viscosity of the melt depending on the component. However, if the introduction amount is too large, there is a risk of deviating from a desired optical constant. Therefore, for ZrO 2 , Al 2 O 3 and Y 2 O 3 , 0 to 1.5% by mass, CaO and SrO, respectively. , K 2 O is suitably kept in the range of 0 to 2% by mass, and the total amount is suitably kept to 5% by mass or less.
モールドプレス用光学ガラスに関しては、前記した特許文献１〜１０のように開示されているものは少なくない。これらの文献に記載されているものは、いずれも本発明が指向する目標に照らして何らかの点で不満足であるが、ガラス組成についても本発明のものと公知のもの（ＰｂＯ，ＣｄＯ，ＢａＯ，Ｔａ2Ｏ5，ＧｅＯ2を必須成分として含むものは除外）とは異なる。例えば
特開２０００−１３２９号公報（特許文献１）に記載の組成はＬａ2Ｏ3の含有量が本発明のものより少なく、一方ＴｉＯ2及びＣａＯの含有量が多い。特開２００２−１７３３３４号公報（特許文献２）記載のものも同様である。特開２０００−１６８３１号公報（特許文献３）に記載のものはＬａ2Ｏ3含有量が少なく、Ｙ2Ｏ3が必須成分であるのに対しＴｉＯ2は必須成分でなく、またＧｄ2Ｏ3も必ずしも必須成分ではない。特許第２９５８９１９号公報（特許文献４）のものではＧｄ2Ｏ3，Ｎｂ2Ｏ5，ＴｉＯ2ともに必須成分ではない。特開２００３−２０１１４３号公報（特許文献５）記載のもの（組成はモル％表示）は、ＴｉＯ2とＮａ2Ｏが必須成分でなく、またＮｂ2Ｏ5も任意成分である。特開２００３−２０１１４２号公報（特許文献６）記載の組成はＳｉＯ2とＬａ2Ｏ3が本発明のものより少なく、これは特許第３３９６４５０号公報（特許文献７）記載のものでも同様である。特開平１１−１３９８４４号公報（特許文献８）、特開平１１−７１１２９号公報（特許文献９）、特開平１１−７９７８１号公報（特許文献１０）等に記載の組成はＢ2Ｏ3が多く、一方Ｇｄ2Ｏ3は必須成分ではない。このように本発明ガラスの成分組成は、前記した開示公報に記載の成分組成とは異なり、まったく新規なものである。
With respect to the optical glass for mold press, there are not a few disclosed as in Patent Documents 1 to 10 described above. All of these documents are unsatisfactory in some respects in light of the goals to which the present invention is directed, but the glass compositions of the present invention and those known (PbO, CdO, BaO, Ta 2 O 5 and GeO 2 as essential components are excluded). For example, the composition described in Japanese Patent Application Laid-Open No. 2000-1329 (Patent Document 1) has a lower content of La 2 O 3 than that of the present invention, while a higher content of TiO 2 and CaO. This is the same as that described in JP-A-2002-173334 (Patent Document 2). JP-A 2000-16831 (Patent Document 3) has a low La 2 O 3 content, Y 2 O 3 is an essential component, whereas TiO 2 is not an essential component, and Gd 2 O 3 is not necessarily an essential component. In Japanese Patent No. 29958919 (Patent Document 4), Gd 2 O 3 , Nb 2 O 5 , and TiO 2 are not essential components. In JP-A-2003-201143 (Patent Document 5) (composition is expressed in mol%), TiO 2 and Na 2 O are not essential components, and Nb 2 O 5 is also an optional component. The composition described in JP 2003-201414 A (Patent Document 6) has less SiO 2 and La 2 O 3 than that of the present invention, and this is the same as that described in Japanese Patent No. 3396450 (Patent Document 7). . The composition described in JP-A-11-139844 (Patent Document 8), JP-A-11-71129 (Patent Document 9), JP-A-11-79781 (Patent Document 10), etc. has a large amount of B 2 O 3. On the other hand, Gd 2 O 3 is not an essential component. Thus, the component composition of the glass of the present invention is completely novel, unlike the component composition described in the above-mentioned disclosure.
〔発明の効果〕
本発明によれば、ガラス融体から直接所望の形状のプリフォームを成形する技術（例えば特願２００２−３３６７４４）において必要な失透に対する十分な安定性を有し、また揮発等に起因する光学定数の変動が少なく、一方環境に有害な成分であるＰｂＯ，ＣｄＯ，ＢａＯを含まないことや高価なＧｅＯ2やＴａ2Ｏ5を用いないことにより、環境に優しく、経済的に有利なガラス組成物を得ることができる。この組成物は短焦点化や小曲率化、また機器の小型化や低価格化に対応するための光学素子（レンズ）材料として好適に使用できる。
〔The invention's effect〕
According to the present invention, there is sufficient stability against devitrification required in a technique (for example, Japanese Patent Application No. 2002-336744) for directly forming a preform having a desired shape from a glass melt, and an optical system caused by volatilization or the like. A glass composition that is environmentally friendly and economically advantageous because it does not contain PbO, CdO, and BaO, which are harmful to the environment, and does not use expensive GeO 2 or Ta 2 O 5. You can get things. This composition can be suitably used as an optical element (lens) material for shortening the focal length, reducing the curvature, and reducing the size and cost of the device.
白金るつぼに、所定量の酸化物（Ｂ2Ｏ3は酸化物のほかＨ2ＢＯ3も使用）、水酸化物、炭酸塩からなる原料混合物を入れ、１３００℃で１．５時間、間欠的に攪拌しながら溶融した。その後、融液を想定されるガラスの転移点より約１００℃下の温度で予め加熱してあるステンレス板上に流しだし、約３０秒経過後、その想定される転移点より約２０℃上に設定されていた電気炉に入れ、３０分間保持した後電源を切って炉内放冷した。冷却後、結晶析出（失透）の有無を調べた。得られたガラスの一部から棒状試料を作製し、ＴＭＡ装置を用いて、５℃／ｍｉｎの昇温速度で熱膨張係数を測定し、定法にしたがって転移点（Ｔｇ）と屈伏点（Ａｔ）を決定した。また、ガラスから一部切り出して研磨した試料を用いてＶブロックプリズム法により屈折率（ｎｄ）と分散（νｄ）を測定した。 A platinum crucible is charged with a predetermined amount of oxide (B 2 O 3 is H 2 BO 3 in addition to oxide), hydroxide and carbonate, and is intermittently used at 1300 ° C. for 1.5 hours. The mixture was melted with stirring. Thereafter, the melt is poured onto a stainless steel plate that is preheated at a temperature about 100 ° C. below the assumed glass transition point, and after about 30 seconds, about 20 ° C. above the assumed transition point. It was put in the set electric furnace, kept for 30 minutes, then turned off and allowed to cool in the furnace. After cooling, the presence or absence of crystal precipitation (devitrification) was examined. A rod-like sample is prepared from a part of the obtained glass, and the thermal expansion coefficient is measured at a rate of temperature increase of 5 ° C./min using a TMA apparatus. It was determined. Further, a refractive index (nd) and dispersion (νd) were measured by a V-block prism method using a sample cut out from glass and polished.
実施したガラスの組成例と物性例を［表１］と［表２］に示す。このうち、［表１］のガラスは本発明のガラス、［表２］のガラスは本発明以外のガラスであるが、本発明は［表１］の組成のみに制約されるものではない。 [Table 1] and [Table 2] show examples of composition and physical properties of the implemented glass. Among these, the glass of [Table 1] is the glass of the present invention, and the glass of [Table 2] is a glass other than the present invention, but the present invention is not limited only to the composition of [Table 1].
（備考）
（１）［表１］及び［表２］中の組成欄の各成分の数字は、バッチ原料から計算した質量％である。
（２）Ｔｇはガラス転移点、Ａｔは屈伏点で、いずれも熱膨張曲線から通常の方法によって決定したものである。
（３）熱膨張係数（α）は１００〜３００℃間の平均値である。
（４）ｎｄは室温におけるｄ線の屈折率、νｄは対応するアッベ数である。（）を付けたのは、失透試料で正確さに欠けるためである。
（５）失透性欄の○は徐冷後のガラスに結晶がまったく認められなかった場合、ｘは肉眼で結晶の析出が明らかな場合、△は肉眼では結晶の析出が不明だが、顕微鏡で精査すると認められた場合を表わす。○印の組成は、本発明が指向する、ガラス融体から直接所望する形状のプリフォームを成形することができるほどの失透に対する安定性を有する。
（６）ガラス番号１２の組成は、失透に対して十分な安定性を有するが、得られるガラスの光学定数が前記屈折率（ｎｄ）１．７〜１．８，アッベ数（νｄ）４４〜４６を満たさない。
(Remarks)
(1) The number of each component in the composition column in [Table 1] and [Table 2] is mass% calculated from the batch raw material.
(2) Tg is the glass transition point and At is the yield point, both of which are determined from the thermal expansion curve by a normal method.
(3) Thermal expansion coefficient ((alpha)) is an average value between 100-300 degreeC.
(4) nd is the refractive index of the d-line at room temperature, and νd is the corresponding Abbe number. The reason for () is that the devitrified sample lacks accuracy.
(5) ○ in the devitrification column indicates that no crystal is observed in the glass after slow cooling, x indicates that crystal precipitation is obvious with the naked eye, and Δ indicates crystal precipitation with the naked eye. Indicates a case where it is recognized that the examination will be conducted. The composition marked with ○ has stability against devitrification to the extent that a preform having a desired shape can be directly formed from a glass melt, to which the present invention is directed.
(6) The composition of glass number 12 has sufficient stability against devitrification, but the optical constants of the obtained glass are the refractive index (nd) 1.7 to 1.8, Abbe number (νd) 44. -46 is not satisfied.
Claims (3)
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| JP4703168B2 (en) * | 2004-11-09 | 2011-06-15 | 株式会社オハラ | Optical glass |
| JP2009208974A (en) * | 2008-02-29 | 2009-09-17 | Ohara Inc | Optical glass, optical element and optical instrument |
| JP5327956B2 (en) * | 2008-11-05 | 2013-10-30 | パナソニック株式会社 | Optical glass composition, preform and optical element |
| JP5946237B2 (en) * | 2010-07-26 | 2016-07-06 | 株式会社オハラ | Optical glass, preform material and optical element |
| CN102765879A (en) * | 2012-06-25 | 2012-11-07 | 成都尤利特光电科技有限公司 | Optical glass with high refractive index and manufacturing method thereof |
| CN103241942B (en) * | 2013-05-24 | 2016-01-13 | 成都尤利特光电科技有限公司 | High-refraction low-dispersion optical glass for mold and manufacture method thereof |
| JP2014196244A (en) * | 2014-07-03 | 2014-10-16 | 株式会社オハラ | Optical glass |
| JP6771811B2 (en) * | 2014-10-29 | 2020-10-21 | 株式会社オハラ | Optical glass, preforms and optics |
| JP6618692B2 (en) * | 2015-03-17 | 2019-12-11 | Hoya株式会社 | Optical glass and optical element |
| CN107879620B (en) * | 2016-09-29 | 2020-12-29 | 成都光明光电股份有限公司 | Optical glass, glass preforms and optical components |
| CN106396369B (en) * | 2016-09-29 | 2017-12-01 | 成都光明光电股份有限公司 | Optical glass, gas preform and optical element |
| JP7148880B2 (en) * | 2017-02-24 | 2022-10-06 | 日本電気硝子株式会社 | optical glass |
| US11958769B2 (en) | 2018-08-17 | 2024-04-16 | Cdgm Glass Co., Ltd. | Optical glass, glass preform or optical element made therefrom, and optical instrument |
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