JPS6114090B2 - - Google Patents
Info
- Publication number
- JPS6114090B2 JPS6114090B2 JP2202379A JP2202379A JPS6114090B2 JP S6114090 B2 JPS6114090 B2 JP S6114090B2 JP 2202379 A JP2202379 A JP 2202379A JP 2202379 A JP2202379 A JP 2202379A JP S6114090 B2 JPS6114090 B2 JP S6114090B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- devitrification resistance
- optical
- optical performance
- 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.)
- Expired
Links
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000005304 optical glass Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004031 devitrification Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 206010040925 Skin striae Diseases 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004369 ThO2 Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
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
- C03C3/04—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
Description
【発明の詳細な説明】
本発明は、屈折率nｄが1.74乃至1.85あり、ア
ツベ数〓ｄが38乃至55の光学性能範囲にあり、酸
化トリウムを全く含まず、しかも耐失透性に優れ
た高屈折率、低分散の光学ガラスに関する。
従来上記した如き光学性能を有する光学ガラス
は、B2O3−La2O3−ThO2系を基礎として作成さ
れて来た。上記基礎系においてThO2を含有せし
めることなく、上記した本発明が目的とする光学
性能範囲を得るためには、La2O3を極めて多量に
含有せしめる必要がある。しかし、La2O3を多量
に含有したガラスは、失透傾向が著しく大きくな
り、これが量産には適さないものとなる。近年で
はThO2を含有せしめず、量産可能な高屈折率、
低分散の光学ガラスを得るべくその研究開発に努
力が払われており、例えばB2O3−La2O3−Gd2O3
系を基礎とし、これに失透防止剤として、
Ta2O5，Y2O3および２価金属酸化物等を導入し
たガラスが知られている。しかしながら、Gd2O3
を多量に含有したガラスは、Gd2O3が近紫外領域
において強い螢光を発するため、高級な光学レン
ズ用の素材としては好ましくない。また、Gd2O3
を含有しないガラスも知られており、特開昭52−
152910号公報に記載されたものは、B2O3−La2O3
−Y2O3系にZnOおよびTa2O5を含有せしめること
によつて、耐失透性を改善せんとしている。しか
しこの場合における失透防止剤として用いられる
Ta2O5は、La2O3とかY2O3に比して、これより高
分散を示すので、ThO2を含有した高屈折率、低
分散ガラスの光学性能範囲を復元することででき
ず、Ta2O5を含有させたものは、ThO2を含有さ
せたものに比して、この点不利である。更に例え
ば、特開昭48−12316号公報記載のものの如く、
B2O3−La2O3−Y2O3系にGeO2或はNb2O5又はそ
の両者を導入することによつて、La2O3とかY2O3
の含有量が多いにもかゝわらず、耐失透性を良好
にしたものも開発されている。しかしこの場合
は、ガラスの粘度が低く、熔融中に揮発が激し
く、そのため脈理を発生し易いという欠点を有す
ることが判つた。
本発明者達は、上記したこれらの欠点を除去
し、量産可能な高屈折率、低分散のガラスについ
て種々研究を行なつた結果、B2O3−La2O3−
Y2O3−ZrO2系にSiO2を導入することによつて、
ガラスの粘度を高め、La2O3およびY2O3の含有量
が多くても耐失透性が良好となり、更にZnOが失
透防止剤として作用すると共に、揮発による脈理
の発生を減少させる特性を有することを知り、こ
の両者の導入によつて量産可能なガラスが得られ
ることを見出した。
従つて、本発明に係る光学ガラスは、重量パー
セントにおいて、下記の組成よりなるものであ
る。すなわち、
SiO2 ２〜５重量％
B2O3 24〜32重量％
ZnO １〜５重量％
ZrO2 １〜10重量％
La2O3 45.1〜55重量％
Y2O3 １〜20重量％
CaO＋PbOの合量 ０〜10重量％
Nb2O5 ０〜20重量％
Li2O＋K2O＋Na2Oの合量 ０〜１重量％
である。
次に各成分を上記重量パーセントの範囲に限定
した理由を示すと下記の通りである。
SiO2は、ガラスの粘度を高めると共に、耐失
透性を良好にする成分であるが、これが２％未満
においては、その効果が殆んど得られず、これが
５％を越すと、逆に耐失透性が悪化するものであ
る。
B2O3は、これを24％以下とすると、耐失透性
が悪化し、これが32％以上となると、本発明が目
的とする光学的性能範囲のものが得られなくな
る。
ZnOは、耐失透性および脈理切れを良好にする
ものであるが、これが１％以下ではその効果が著
しく低下し、これが５％以上となると、本発明が
目的とする光学的性能範囲のものが得られなくな
る。
ZrO2は、失透に対して安定な成分であるが、
これが１％以下、また10％以上となると、その効
果は著しく低下する。
La2O3は、これが45.1％以下となると、本発明
が目的とする光学的性能範囲に達しなくなり、こ
れが55％以上となると、耐失透性が急激に悪化す
る。
Y2O3は、高屈折率、低分散成分中でも、特に
失透に対して安定な成分であるが、これを１％以
下にすると、その効果が得られず、これを20％以
上にすると、逆に耐失透性を悪化する。
またCaOとかPbOは、光学性能およびガラスの
粘度を調整するために使用することができるが、
その１成分またはこれらの合計量を10％以上にす
ると耐失透性を悪化させる。
Nb2O5は、高屈折率のガラスを得るために使用
することができるが、これが20％以上となると、
分散が大きくなり、加えて耐失透性も悪化する。
Li2O，K2O，Na2Oは、これをガラスの清澄剤
として添加することができるが、その１成分また
は２成分以上の合計量を１％以上にすると、耐失
透性を悪化させる。WO3は、光学的性能を調整
するために使用することができるが、これが10％
以上になると着色が著しくなる。
本発明において、光学ガラスの各成分の原料
は、SiO2，ZnO，ZrO2，La2O3，Y2O3，WO3お
よびNb2O5は、夫々の酸化物を用い、B2O3は硼酸
を用い、PbOは鉛丹を用い、CaO，Li2O，Na2O
はその炭酸塩を用い、K2Oは硝酸塩を用いた。こ
れらの材料の混合物を通例のような白金容器にて
1250℃乃至1350℃で熔解、清澄、撹拌を行ない、
適当な温度に予熱された鋳型に注入し、これを徐
冷することによつて、製造することができる。
このようにして製造されたガラスは、無色であ
つて、透明度が高く、しかも化学的耐久性に優れ
ている。
本発明に係る光学ガラスの実施例を次表により
示す。
【表】[Detailed Description of the Invention] The present invention has a refractive index n d of 1.74 to 1.85, an Atsube number d in the range of 38 to 55, has an optical performance range of 38 to 55, does not contain any thorium oxide, and has excellent devitrification resistance. This invention relates to optical glasses with high refractive index and low dispersion. Conventionally, optical glasses having the optical performance as described above have been produced based on the B2O3 - La2O3 - ThO2 system. In order to obtain the optical performance range targeted by the present invention described above without containing ThO 2 in the basic system, it is necessary to contain an extremely large amount of La 2 O 3 . However, glass containing a large amount of La 2 O 3 has a marked tendency to devitrify, making it unsuitable for mass production. In recent years, high refractive index, which does not contain ThO 2 and can be mass-produced,
Efforts are being made in research and development to obtain optical glasses with low dispersion, such as B 2 O 3 −La 2 O 3 −Gd 2 O 3
Based on this system, as an anti-devitrification agent,
Glasses containing Ta 2 O 5 , Y 2 O 3 and divalent metal oxides are known. However, Gd 2 O 3
Glass containing a large amount of Gd 2 O 3 is not preferred as a material for high-grade optical lenses because Gd 2 O 3 emits strong fluorescence in the near-ultraviolet region. Also, Gd 2 O 3
There is also known glass that does not contain
What is described in Publication No. 152910 is B 2 O 3 −La 2 O 3
- By incorporating ZnO and Ta 2 O 5 into the Y 2 O 3 system, it is attempted to improve the devitrification resistance. However, in this case it is used as an anti-devitrification agent.
Since Ta 2 O 5 exhibits higher dispersion than La 2 O 3 or Y 2 O 3 , it is possible to restore the optical performance range of high refractive index, low dispersion glass containing ThO 2 . First, those containing Ta 2 O 5 are disadvantageous in this respect compared to those containing ThO 2 . Furthermore, for example, as described in JP-A-48-12316,
By introducing GeO 2 or Nb 2 O 5 or both into the B 2 O 3 −La 2 O 3 −Y 2 O 3 system, La 2 O 3 or Y 2 O 3
Even though the content is high, products with good devitrification resistance have also been developed. However, it has been found that this case has the disadvantage that the glass has a low viscosity and volatilizes violently during melting, making it easy to generate striae. The present inventors have conducted various studies on high refractive index, low dispersion glass that can be mass-produced by eliminating these drawbacks described above, and as a result, B 2 O 3 −La 2 O 3 −
By introducing SiO 2 into the Y 2 O 3 −ZrO 2 system,
Increases the viscosity of the glass, resulting in good devitrification resistance even with high contents of La 2 O 3 and Y 2 O 3 , and ZnO acts as an anti-devitrification agent and reduces the occurrence of striae due to volatilization. They discovered that by introducing both of these characteristics, a glass that can be mass-produced can be obtained. Therefore, the optical glass according to the present invention has the following composition in weight percent. That is, SiO 2 2-5% by weight B 2 O 3 24-32% by weight ZnO 1-5% by weight ZrO 2 1-10% by weight La 2 O 3 45.1-55% by weight Y 2 O 3 1-20% by weight CaO+PbO The total amount of Nb2O5 is 0 to 20% by weight, and the total amount of Li2O + K2O + Na2O is 0 to 1% by weight. Next, the reason why each component is limited to the above weight percentage range is as follows. SiO 2 is a component that increases the viscosity of glass and improves its devitrification resistance, but if it is less than 2%, it will hardly have any effect, and if it exceeds 5%, it will The devitrification resistance deteriorates. When B 2 O 3 is 24% or less, the devitrification resistance deteriorates, and when it is 32% or more, the optical performance range targeted by the present invention cannot be obtained. ZnO improves devitrification resistance and striae breakage, but if it is less than 1%, the effect will be significantly reduced, and if it is more than 5%, it will fall outside the optical performance range targeted by the present invention. You won't be able to get anything. ZrO 2 is a stable component against devitrification, but
If this becomes less than 1% or more than 10%, the effect will be significantly reduced. When La 2 O 3 is less than 45.1%, it does not reach the optical performance range targeted by the present invention, and when it is more than 55%, the devitrification resistance deteriorates rapidly. Y 2 O 3 is a component that is particularly stable against devitrification among high refractive index and low dispersion components, but if it is less than 1%, the effect cannot be obtained, and if it is more than 20%, On the contrary, the devitrification resistance deteriorates. CaO and PbO can also be used to adjust the optical performance and viscosity of the glass.
If the amount of one component or the total amount of these components exceeds 10%, the devitrification resistance will deteriorate. Nb2O5 can be used to obtain glasses with high refractive index, but when this is more than 20%,
Dispersion increases, and devitrification resistance also deteriorates. Li 2 O, K 2 O, and Na 2 O can be added as glass refining agents, but if the total amount of one or more of these components exceeds 1%, the devitrification resistance will deteriorate. let WO3 can be used to adjust the optical performance, but this is 10%
If the amount exceeds that amount, the coloring becomes noticeable. In the present invention, the raw materials for each component of optical glass are SiO 2 , ZnO, ZrO 2 , La 2 O 3 , Y 2 O 3 , WO 3 and Nb 2 O 5 using their respective oxides, and B 2 O 3 uses boric acid, PbO uses red lead, CaO, Li 2 O, Na 2 O
used its carbonate, and K 2 O used its nitrate. A mixture of these materials is placed in a platinum container such as customary.
Melt, clarify, and stir at 1250℃ to 1350℃,
It can be manufactured by pouring into a mold preheated to an appropriate temperature and slowly cooling the mold. The glass thus produced is colorless, highly transparent, and has excellent chemical durability. Examples of optical glasses according to the present invention are shown in the following table. 【table】
Claims (1)
高屈折率低分散の光学的性能を有する光学ガラ
ス： SiO2 ２〜５重量％ B2O3 24〜32重量％ ZnO １〜５重量％ ZrO2 １〜10重量％ La2O3 45.1〜55重量％ Y2O3 １〜20重量％ CaO＋PbOの合量 ０〜10重量％ Nb2O5 ０〜20重量％ Li2O＋K2O＋Na2Oの合量 ０〜１重量％[Claims] 1. Optical glass having optical performance with high refractive index and low dispersion and having the following composition in weight percent: SiO 2 2-5% by weight B 2 O 3 24-32% by weight ZnO 1-5% by weight % ZrO 2 1-10% by weight La 2 O 3 45.1-55% by weight Y 2 O 3 1-20% by weight Total amount of CaO + PbO 0-10% by weight Nb 2 O 5 0-20% by weight Li 2 O + K 2 O + Na 2 Total amount of O: 0 to 1% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2202379A JPS55116641A (en) | 1979-02-28 | 1979-02-28 | Optical glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2202379A JPS55116641A (en) | 1979-02-28 | 1979-02-28 | Optical glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55116641A JPS55116641A (en) | 1980-09-08 |
| JPS6114090B2 true JPS6114090B2 (en) | 1986-04-17 |
Family
ID=12071377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2202379A Granted JPS55116641A (en) | 1979-02-28 | 1979-02-28 | Optical glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55116641A (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4017832B2 (en) * | 2001-03-27 | 2007-12-05 | Ｈｏｙａ株式会社 | Optical glass and optical components |
| JP4562041B2 (en) * | 2002-12-27 | 2010-10-13 | Ｈｏｙａ株式会社 | Optical glass, glass gob for press molding, and optical element |
| DE102004009930B4 (en) * | 2004-02-26 | 2008-07-24 | Schott Ag | Lead- and arsenic-free optical lanthanum flint glasses and their use |
| US7576020B2 (en) | 2004-10-12 | 2009-08-18 | Hoya Corporation | Optical glass, precision press-molding preform, process for the production of the preform, optical element and process for the production of the optical element |
| JP2008222479A (en) * | 2007-03-12 | 2008-09-25 | Ohara Inc | Optical glass |
| JP2008233547A (en) * | 2007-03-20 | 2008-10-02 | Hoya Corp | Lens glass material for on-vehicle camera and lens for on-vehicle camera |
| CN102311229A (en) * | 2011-09-07 | 2012-01-11 | 成都光明光电股份有限公司 | 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 |
| CN107721160A (en) * | 2013-04-05 | 2018-02-23 | 株式会社小原 | Optical glass, preforming material and optical element |
| JP6188553B2 (en) * | 2013-07-31 | 2017-08-30 | 株式会社オハラ | Optical glass, preform material and optical element |
| JP6049591B2 (en) * | 2013-07-31 | 2016-12-21 | 株式会社オハラ | Optical glass, preform material and optical element |
| JP5979723B2 (en) * | 2013-07-31 | 2016-08-31 | 株式会社オハラ | Optical glass and optical element |
| JP6544238B2 (en) * | 2013-12-03 | 2019-07-17 | Ａｇｃ株式会社 | Optical glass, preform for press molding and optical element |
| JP6603449B2 (en) | 2014-09-30 | 2019-11-06 | Ｈｏｙａ株式会社 | Glass, glass material for press molding, optical element blank, and optical element |
| JP6033487B2 (en) * | 2016-08-19 | 2016-11-30 | 株式会社オハラ | Optical glass and optical element |
| JP7174536B2 (en) * | 2017-05-16 | 2022-11-17 | 株式会社オハラ | Optical glass, preforms and optical elements |
| JP2017171578A (en) * | 2017-06-23 | 2017-09-28 | 株式会社オハラ | Optical glass and optical element |
| JP6600702B2 (en) * | 2018-01-18 | 2019-10-30 | Ｈｏｙａ株式会社 | Glass, glass material for press molding, optical element blank, and optical element |
| JP7089933B2 (en) * | 2018-04-26 | 2022-06-23 | Hoya株式会社 | Optical glass and optical elements |
-
1979
- 1979-02-28 JP JP2202379A patent/JPS55116641A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55116641A (en) | 1980-09-08 |
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