JP3347106B2 - Lead-free optical glass - Google Patents
Lead-free optical glassInfo
- Publication number
- JP3347106B2 JP3347106B2 JP29477799A JP29477799A JP3347106B2 JP 3347106 B2 JP3347106 B2 JP 3347106B2 JP 29477799 A JP29477799 A JP 29477799A JP 29477799 A JP29477799 A JP 29477799A JP 3347106 B2 JP3347106 B2 JP 3347106B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- lead
- optical glass
- glass
- free
- 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 - Lifetime
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、1.64〜1.8
3の屈折率nd及び36〜56のアッベ数νdを有する無
鉛光学ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a lead-free optical glass having a refractive index n d of 3 and an Abbe number v d of 36 to 56.
【0002】[0002]
【従来の技術】近年、ガラス成分PbO及びAs2O3は
環境汚染物質として話題になってきているため、光学機
器の製造業者の中では、PbOを含有せず、さらに好ま
しくはAs2O3も含有しない、所定の光学的性質を有す
るガラスが求められている。単に酸化鉛を1つ又はそれ
以上の成分で置換するだけでは、光学的性質及びガラス
技術上の性質はPbOの影響を受けるため、一般に、そ
のような所望の性質を有するガラスを再現することはで
きない。従って、それに代って、新規なガラス組成を開
発すること、又は少なくともかなりの変更を行なうこと
が必要となる。 2. Description of the Related Art In recent years, glass components PbO and As 2 O 3 have become a hot topic as environmental pollutants. Therefore, some optical device manufacturers do not contain PbO, and more preferably As 2 O 3. There is a demand for a glass having predetermined optical properties which does not contain any. Simply replacing the lead oxide with one or more components is generally not enough to reproduce a glass having such desired properties because the optical and glass technical properties are affected by PbO. Can not. Therefore, it is necessary to develop new glass compositions instead, or at least make considerable changes.
【0003】種々の仕様が以下に挙げる特許文献に既に
示されており、上記範囲にある光学値を有する無鉛ガラ
スが記載されている。しかしながら、これらのガラスは
多様な欠点を有する。Various specifications have already been described in the patent documents listed below, and lead-free glass having an optical value in the above range is described. However, these glasses have various disadvantages.
【0004】ドイツ特許第2265703号及び米国特
許第3958999号は、B2O3−Gd2O3−La2O3
系からなる光学ガラスを開示している。このガラスは失
透に対して安定化させるために、少なくとも2質量%及
び50質量%までのGd2O3を必要とする。この高価な
成分が大量に存在することにより、ガラスがより高価な
ものとなる。特別な態様において、米国特許第3958
999号に開示されたガラスは少なくとも2質量%の同
じように高価な成分Ta2O5を付加的に含有する。[0004] German Patent No. 2,265,703 and US Pat. No. 3,958,999 disclose B 2 O 3 -Gd 2 O 3 -La 2 O 3.
An optical glass comprising a system is disclosed. This glass requires at least 2% by weight and up to 50% by weight of Gd 2 O 3 to be stabilized against devitrification. The presence of large amounts of this expensive component makes the glass more expensive. In a particular embodiment, US Pat.
The glass disclosed in 999 additionally contains at least 2% by weight of a similarly expensive component Ta 2 O 5 .
【0005】特開昭61−146730号及び特開昭6
0−221338号に記載のガラスは、失透傾向を増加
させるLi2Oを必須成分として含有する。後に挙げた
明細書に記載されたガラスは、所望の屈折率ndを得る
ために、共に高価な成分である20質量%までのY2O3
及び52質量%までのLa2O3を付加的に必要とするこ
とから、ガラスが高価なものになり、またタンクでの製
造が不経済となる。[0005] JP-A-61-146730 and JP-A-6-146730
The glass described in 0-221338 contains Li 2 O, which increases the tendency to devitrify, as an essential component. In order to obtain the desired index of refraction n d , the glasses described in the later-mentioned specification have a high content of Y 2 O 3 up to 20% by weight, both of which are expensive components.
And the additional requirement of up to 52% by weight of La 2 O 3 makes the glass expensive and uneconomical to manufacture in tanks.
【0006】ドイツ特許第3201344号は、高屈折
率のガラスを開示しており、15〜22質量%の(Ti
O2+Nb2O5+Y2O3)と、高い割合で溶融性付与剤
(TiO2)及び高価な成分(Nb2O5、Y2O3)を含
有し、また大量のCaO(4〜18質量%)を含有し、
一方、BaOは最大量が14質量%の唯一任意的な成分
である。German Patent No. 3,201,344 discloses a glass of high refractive index, with 15 to 22% by weight of (Ti
O 2 + Nb 2 O 5 + Y 2 O 3) and contains a melt-imparting agent in a high proportion (TiO 2) and expensive component (Nb 2 O 5, Y 2 O 3), also a large amount of CaO (. 4 to 18% by mass)
On the other hand, BaO is the only optional component with a maximum amount of 14% by mass.
【0007】[0007]
【発明が解決しようとする課題】本発明の目的は、経済
的に製造でき、良好な溶融及び加工特性を有し、1.6
4〜1.83の屈折率nd及び36〜56のアッべ数νd
を有する無鉛光学ガラスを提供することにある。本発明
の目的には、適当な結晶化安定性を得ることも含まれ
る。SUMMARY OF THE INVENTION It is an object of the present invention to provide an economical production, good melting and processing properties, and 1.6
Refractive index n d of 4 to 1.83 and Abbe number ν d of 36 to 56
The object of the present invention is to provide a lead-free optical glass having: The purpose of the present invention also includes obtaining suitable crystallization stability.
【0008】[0008]
【課題を解決するための手段】本発明によれば、上記目
的を達成するために、酸化物基準で以下の量的割合で以
下の成分 SiO2 10〜25質量%、B2O3 8〜20質量%、 ZrO2 1〜5質量%、TiO2 1〜5質量%、 La2O3 10〜30質量%、BaO 30〜50質量%、 ZnO 0.1〜2質量%、CaO 0.5〜2質量%、 WO3 0.1〜2質量%、Nb2O5 0.1〜5質量%、 Y2O3 0.1〜3質量%、Gd2O3 0〜1質量%、 Na2O 0〜1質量%、K2O 0〜1質量%、 を含有し、Li 2 Oを含有しないことを特徴とする1.
64〜1.83の屈折率nd及び36〜56のアッベ数
νdを有する無鉛光学ガラスが提供される。この無鉛光
学ガラスは、必要に応じて慣用量の清澄剤を含有するこ
とができる。 According to the present invention, in order to achieve the above object, the following quantitative ratios based on oxides are used.
Components SiO 2 10 to 25% by weight below, B 2 O 3 8~20 wt%, ZrO 2 1 to 5 wt%, TiO 2 1 to 5 wt%, La 2 O 3 10~30% by weight, BaO. 30 to 50 wt%, ZnO 0.1 to 2 wt%, CaO 0.5 to 2 wt%, WO 3 0.1 to 2 wt%, Nb 2 O 5 0.1~5 wt%, Y 2 O 3 0. 1-3 wt%, Gd 2 O 3 0 to 1 wt%, Na 2 O 0 to 1 wt%, K 2 O 0 to 1 wt%, the a free, characterized in that it does not contain Li 2 O 1.
A lead-free optical glass having a refractive index n d of 64-1.83 and an Abbe number v d of 36-56 is provided. This lead-free light
The glass should contain conventional amounts of fining agents as necessary.
Can be.
【0009】[0009]
【発明の実施の形態】本発明のガラスは、ガラス形成剤
SiO2(10〜25質量%)及びB2O3(8〜20質
量%)をバランスのとれた割合で含有する。従って、ガ
ラスの溶融特性(B2O3含量を増加させることにより改
善され、SiO2含量を増加させることにより低下す
る)、及び耐薬品性(過剰のB2O3含量により損なわれ
るであろう。)の両者が良好である。前記の最小B2O3
含量を減らすことにより、失透傾向が顕著に増すであろ
う。BEST MODE FOR CARRYING OUT THE INVENTION The glass of the present invention contains glass forming agents SiO 2 (10 to 25% by mass) and B 2 O 3 (8 to 20% by mass) in a balanced ratio. Thus, the melting properties of the glass (improved by increasing the B 2 O 3 content and reduced by increasing the SiO 2 content), and chemical resistance (will be impaired by the excess B 2 O 3 content). )) Are good. The minimum B 2 O 3
Decreasing the content will significantly increase the tendency to devitrification.
【0010】本発明のガラスは30〜50質量%のBa
Oを含有する。所望されるアッベ数を得るためには、こ
のBaO含量が必要となる。特に、BaO含量に対する
B2O3及びSiO2の含量のバランスがとれているため
に、本発明のガラスの溶融特性は特に良好である。Ba
Oの他に、本発明のガラスは0.5〜2質量%のCaO
及び0.1〜2質量%のZnOを含有する。BaOと一
緒にこれらが存在することで、ガラスの結晶化安定性が
改善される。The glass of the present invention has a Ba content of 30 to 50% by mass.
Contains O. This BaO content is required to obtain the desired Abbe number. In particular, the melting properties of the glasses according to the invention are particularly good, because of the balance of the B 2 O 3 and SiO 2 content with respect to the BaO content. Ba
In addition to O, the glass of the present invention has a CaO content of 0.5-2% by weight.
And 0.1 to 2% by mass of ZnO. The presence of these together with BaO improves the crystallization stability of the glass.
【0011】本発明のガラスはTiO2及びZrO2の両
者をそれぞれ1〜5質量%の割合で含有する。これらの
2成分は耐薬品性、特に耐アルカリ性を改善する。含量
が高くなるほど結晶化安定性が減少するであろう。特に
好ましくは本発明のガラスはZrO2とTiO2を同じ様
な割合で含有し、このことは、好ましいZrO2/Ti
O2の質量比が0.8〜1.0であることによって表わ
すことができる。The glass of the present invention contains both TiO 2 and ZrO 2 at a ratio of 1 to 5% by mass. These two components improve the chemical resistance, especially the alkali resistance. Higher content will decrease crystallization stability. Particularly preferably, the glasses according to the invention contain similar proportions of ZrO 2 and TiO 2, which means that the preferred ZrO 2 / Ti
It can be represented by a mass ratio of O 2 of 0.8 to 1.0.
【0012】本発明のガラスは10〜30質量%のLa
2O3を含有する。この範囲において所望の光学特性、特
に適度なアッベ数と共に高い屈折率が得やすくなる。さ
らに、La2O3はガラスの透過性を増加させ、またそれ
らの結晶化安定性を促進する。La2O3含量を増やすほ
ど屈折率nd及びアッベ数νdが変化し、またバッチが必
要以上に高価になるであろう。The glass of the present invention has a La content of 10 to 30% by mass.
Contains 2 O 3 . Within this range, it becomes easy to obtain desired optical characteristics, particularly a high refractive index with an appropriate Abbe number. In addition, La 2 O 3 increases the permeability of the glasses and promotes their crystallization stability. Increasing the La 2 O 3 content will change the refractive index n d and Abbe number ν d and will make the batch more expensive than necessary.
【0013】高い屈折率における低いアッベ数を変化さ
せたり、正確に合わすために、本発明のガラスは、0.
1〜2質量%のWO3、0.1〜5質量%のNb2O5及
び0.1〜3質量%のY2O3を含有し、また1質量%ま
でGd2O3を含有することができる。これらの4成分の
合計量は好ましくは5質量%よりも多い。In order to change or precisely match the low Abbe number at high refractive indices, the glass of the present invention has a.
1-2% by weight of WO 3, contains Nb 2 O 5 and 0.1 to 3 wt% of Y 2 O 3 of 0.1 to 5 mass%, also contains Gd 2 O 3 up to 1 wt% be able to. The total amount of these four components is preferably greater than 5% by weight.
【0014】溶融特性をさらに改善するために、本発明
のガラスはまたNa2Oを1質量%まで及びK2Oを1質
量%まで含有することができる。この範囲より含量が高
くなると、結晶化傾向が増加するであろう。同じ理由に
よりLi2Oは全く含有しない。To further improve the melting properties, the glasses according to the invention can also contain up to 1% by weight of Na 2 O and up to 1% by weight of K 2 O. If the content is higher than this range, the tendency to crystallize will increase. For the same reason, Li 2 O is not contained at all.
【0015】前記の組成範囲内において、ガラスは屈折
率により以下の2つの群に分類される。第一群は1.6
4〜1.75の屈折率ndを有するガラスであって、少
なくとも25質量%の(SiO2+B2O3)及び最高で
60質量%の(BaO+La2O 3)を含有するものであ
る(但し、La2O3の最大量は25質量%である。)。
第二群は1.75〜1.83の屈折率ndを有するガラ
スであって、最高で25質量%の(SiO2+B
2O3)、10〜17質量%のSiO2及び8〜15質量
%のB2O3並びに少なくとも60質量%の(BaO+L
a2O3)を含有するものである(但し、La2O3含量は
少なくとも15質量%である。)。In the above composition range, the glass is refracted.
It is divided into the following two groups according to the rate. The first group is 1.6
Refractive index n of 4 to 1.75dGlass with
At least 25% by mass of (SiOTwo+ BTwoOThree) And at most
60% by mass of (BaO + LaTwoO Three)
(However, LaTwoOThreeIs 25% by mass. ).
The second group has a refractive index n of 1.75 to 1.83.dGala with
And up to 25% by weight of (SiO 2Two+ B
TwoOThree), 10 to 17% by mass of SiOTwoAnd 8 to 15 mass
% BTwoOThreeAnd at least 60% by weight of (BaO + L
aTwoOThree) (However, LaTwoOThreeContent
It is at least 15% by mass. ).
【0016】請求項1に記載の組成範囲の中に、1.7
1〜1.75の屈折率nd及び42〜46のアッベ数νd
を有するガラスの1群があり、これらは耐薬品性及び結
晶化安定性に特徴がある。これらのガラスは酸化物基準
で以下の組成を有する。 SiO2 15〜21質量%(特に好ましくは15〜17質量%)、 B2O3 10〜15質量%(特に好ましくは12〜15質量%)、 ZrO2 1〜4質量%(特に好ましくは2〜3質量%)、 TiO2 1〜4質量%(特に好ましくは2〜3質量%)、 好ましくはSiO2+ZrO2+TiO2 19〜23質量%、 La2O3 15〜25質量%(特に好ましくは19〜22質量%)、 BaO 30〜43質量%(特に好ましくは37〜39質量%)、 ZnO 0.1〜1質量%、 CaO 0.5〜1質量%、 但し、BaO+ZnO+CaO≧31質量%(好ましくは37.6〜41質量 %)、 WO3 0.1〜1質量%、 Nb2O5 2〜5質量%(特に好ましくは2〜4質量%)、 Y2O3 0.1〜2質量%(特に好ましくは0.5〜1.5質量%)、 Gd2O3 0〜1質量%、 但し、Y2O3+Gd2O3≧0.2質量%(好ましくは≧0.6〜2.5質量% )、 Na2O 0〜1質量%、K2O 0〜1質量% 前記の好ましい組成を有するガラスは、1.73〜1.
75の屈折率nd及び44〜46のアッベ数νdの光学的
データを有していた。In the composition range according to claim 1, 1.7 is used.
Refractive index n d of 1-1.75 and Abbe number v d of 42-46
There is a group of glasses having the following properties: they are characterized by chemical resistance and crystallization stability. These glasses have the following composition on an oxide basis: SiO 2 15 to 21% by mass (particularly preferably 15 to 17% by mass), B 2 O 3 10 to 15% by mass (particularly preferably 12 to 15% by mass), ZrO 2 1 to 4% by mass (particularly preferably 2 to 15% by mass) to 3 wt%), TiO 2 1 to 4% by weight (particularly preferably 2 to 3 wt%), preferably SiO 2 + ZrO 2 + TiO 2 19~23 wt%, La 2 O 3 15-25% by weight (particularly preferably Is 19 to 22% by mass), BaO is 30 to 43% by mass (particularly preferably 37 to 39% by mass), ZnO is 0.1 to 1% by mass, CaO is 0.5 to 1% by mass, provided that BaO + ZnO + CaO ≧ 31% by mass. (preferably 37.6 to 41 mass%), WO 3 0.1 to 1 wt%, Nb 2 O 5 2~5 wt% (particularly preferably 2 to 4 wt%), Y 2 O 3 0.1~ 2% by mass (particularly preferably 0.5 to 1.5 Mass%), Gd 2 O 3 0 to 1 mass%, provided that Y 2 O 3 + Gd 2 O 3 ≧ 0.2 mass% (preferably ≧ 0.6 to 2.5 mass%), Na 2 O 0 to 0 mass% 1 mass%, the glass having a preferred composition of K 2 O 0 to 1 wt% above, 1.73 to 1.
It had optical data of a refractive index n d of 75 and Abbe number v d of 44-46.
【0017】SiO2とB2O3の総質量と、BaO、Z
nO及びCaOの総質量の比((SiO2+B2O3)/
(BaO+ZnO+CaO))は、好ましくは0.5〜
1である。この範囲内で、ガラスの結晶化安定性が特に
良好となる。特に前記の好ましいガラス(1.71≦n
d≦1.75、42≦νd≦46)の質量比は、≦1が特
に都合が良く、少なくとも0.5の好ましい最小値を満
たす。前記の特に好ましいガラス(1.73≦nd≦
1.75、44≦νd≦46)は、この好ましい質量比
を満たすバランスのとれた成分組成をすでに有してい
る。The total mass of SiO 2 and B 2 O 3 , BaO, Z
Ratio of the total mass of nO and CaO ((SiO 2 + B 2 O 3 ) /
(BaO + ZnO + CaO)) is preferably 0.5 to
It is one. Within this range, the crystallization stability of the glass becomes particularly good. Particularly, the preferred glass (1.71 ≦ n)
As for the mass ratio of d ≦ 1.75, 42 ≦ ν d ≦ 46), ≦ 1 is particularly convenient and satisfies a preferable minimum value of at least 0.5. The above particularly preferred glass (1.73 ≦ n d ≦
1.75, 44 ≦ ν d ≦ 46) already have a balanced component composition that satisfies this preferred mass ratio.
【0018】ガラスの品質を改善するために、それ自体
公知の1種又はそれよりも多くの清澄剤を慣用の量でバ
ッチに加えることによりガラスを清澄することができ
る。これによりガラスは泡や筋のない特に良好な内部品
質を有する。使用する清澄剤がAs2O3でなく、その換
わりに例えばガラス品質を損なうことなく清澄可能なS
b2O3である場合、本発明の無鉛ガラスはさらにヒ素を
含有しないものとなる。Sb2O3含量は好ましくは0.
1〜0.5質量%である。さらに好ましいガラスは、S
b2O3の他に任意に、同様の清澄作用のあるフッ化物を
0.5質量%まで含有する。フッ化物は例えばCaF2
又はNaFとして加えられる。To improve the quality of the glass, the glass can be refined by adding one or more fining agents known per se to the batch in conventional amounts. The glass thereby has a particularly good internal quality without bubbles and streaks. The fining agent used is not As 2 O 3 , but instead, for example, S which can be refined without impairing the glass quality
When b 2 O 3 is used, the lead-free glass of the present invention does not further contain arsenic. The Sb 2 O 3 content is preferably 0.
1 to 0.5% by mass. More preferred glass is S
Optionally, in addition to b 2 O 3 , up to 0.5% by weight of a similar fining fluoride. Fluoride is, for example, CaF 2
Or added as NaF.
【0019】[0019]
【実施例】以下、実施例を示して本発明についてさらに
具体的に説明するが、本発明が下記実施例に限定されな
いことはもとよりである。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but it is needless to say that the present invention is not limited to the following examples.
【0020】実施例1〜9 本発明の9つの実施例の新規なガラスを慣用の原料から
製造した。表1に溶解例の一つ(表2の実施例3)を示
す。Examples 1 to 9 The novel glasses of the nine examples of the present invention were prepared from conventional raw materials. Table 1 shows one of the dissolution examples (Example 3 in Table 2).
【0021】[0021]
【表1】 [Table 1]
【0022】表2に、製造された各実施例のガラスのそ
れぞれの組成(酸化物基準の質量%表示)、屈折率
nd、アッベ数νd、スペクトルの青色領域における部分
分散Pg, F及び異常部分分散(この部分分散の標準直線
からの偏差)ΔPg,F[10-4]、密度ρ[g/c
m3]、熱膨張率α20/300[10-6/K]及びガラス転移
温度Tg[℃]を示す。Table 2 shows the respective compositions (expressed in mass% based on oxides), refractive indices n d , Abbe numbers ν d , and partial dispersions P g, F in the blue region of the spectrum of the glasses of the respective examples produced. And anomalous partial variance (deviation of this partial variance from the standard line) ΔP g, F [10 −4 ], density ρ [g / c
m 3 ], coefficient of thermal expansion α 20/300 [10 −6 / K], and glass transition temperature Tg [° C.].
【0023】[0023]
【表2】 [Table 2]
【0024】本発明のガラスは以下のようにして製造し
た。すなわち、清澄剤を酸化物用の原料、好ましくは炭
酸塩及び硝酸塩に加えてよく攪拌した。ガラスバッチを
バッチ溶解装置内で約1,220〜1,360℃で溶解
し、次いで清澄化し、充分に均質化した。注型温度は約
1,050℃であった。The glass of the present invention was produced as follows. That is, the fining agent was added to a raw material for an oxide, preferably a carbonate and a nitrate, and the mixture was stirred well. The glass batch was melted in a batch melting apparatus at about 1,220-1360 ° C., then clarified and homogenized well. The casting temperature was about 1,050 ° C.
【0025】実施例6及び7の組成物の組成は、特許請
求した組成の上限及び下限に近く、また実施例の中で、
屈折率及びアッベ数が両極端な数値、即ちいずれか一方
が最小値の場合、他方は最大値を示していた。しかしな
がら、それらの物理的特性は、好ましい組成範囲の中か
らより狭い範囲を特定したガラスの物理的特性と同様で
あった。The compositions of the compositions of Examples 6 and 7 are close to the upper and lower limits of the claimed composition and, in the Examples,
When the refractive index and Abbe number were extreme values, that is, when one of them was the minimum value, the other showed the maximum value. However, their physical properties were similar to those of glasses that specified a narrower range from the preferred composition range.
【0026】[0026]
【発明の効果】本発明のガラスは所望の光学特性の他
に、以下の有利な点を有する。本発明のガラスはPbO
を含有せず、好ましい態様においてはAs2O3も含有し
ていない。本発明のガラスは良好な結晶化安定性を有す
る。これにより連続装置で製造が可能となる。このタイ
プの製造にとって適切な結晶化安定性の尺度は失透上限
における粘度である。連続生産するためには、1000
dPas以上あるべきである。本発明のガラスはこの要
件を満たしている。当該ガラスの結晶化安定性により、
ガラスの熱処理、例えば加圧又は再加圧をさらに行うこ
とも可能となる。本発明のガラスは、良好な加工特性だ
けでなくまた良好な溶融特性を有する。このことはまた
約1300℃の融点により示される。 本発明のガラス
は、耐アルカリ性がAR=1のクラスに分類されること
が立証されている通り、優れた耐アルカリ性を有してお
り、また同時に適切な一般的な耐薬品性も有する。本発
明のガラスの耐薬品性は例えば研削及び磨きをさらに行
う上で重要なものである。The glass of the present invention has the following advantages in addition to the desired optical properties. The glass of the present invention is PbO
And in a preferred embodiment, it does not contain As 2 O 3 . The glasses of the present invention have good crystallization stability. This allows production with a continuous device. A suitable measure of crystallization stability for this type of production is the viscosity at the upper devitrification limit. For continuous production, 1000
Should be dPas or more. The glass of the present invention meets this requirement. Due to the crystallization stability of the glass,
A further heat treatment of the glass, for example pressurization or repressurisation, is also possible. The glasses of the invention have not only good processing properties but also good melting properties. This is also indicated by a melting point of about 1300 ° C. The glasses of the present invention have excellent alkali resistance, as demonstrated by the fact that the alkali resistance is classified in the class of AR = 1, and at the same time have suitable general chemical resistance. The chemical resistance of the glass of the present invention is important, for example, for further grinding and polishing.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 ダヌータ グラボウスキー ドイツ連邦共和国、65232 タウヌスシ ュタイン−ヴィングスバッハ、フォル デム キルヒホルスト 16アー (72)発明者 マグダレナ、ヴィンクレル−トゥルーデ ヴィッヒ ドイツ連邦共和国、55126 マインツ、 アム・キルヒボーン 20ベー (72)発明者 ジルケ ヴォルフ ドイツ連邦共和国、42499 ヒュッケス ワーゲン、ヒュッキンガー・シュトラー セ 47アー (56)参考文献 特開 昭60−221338(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 Continued on the front page (72) Inventor Danuta Graboski, Germany, 65232 Taunus-Stuin-Wingsbach, Fordem Kirchhorst 16 a Am Kirchborn 20B (72) Inventor Silke Wolf 42, Hückes Wagen, Hückinger Strasse 47er, Germany 48, 56 References JP-A-60-221338 (JP, A) JP-A 62-100449 (JP , A) (58) Fields investigated (Int. Cl. 7 , DB name) C03C 1/00-14/00
Claims (12)
分 SiO2 10〜25質量%、B2O3 8〜20質量%、 ZrO2 1〜5質量%、TiO2 1〜5質量%、 La2O3 10〜30質量%、BaO 30〜50質量%、 ZnO 0.1〜2質量%、CaO 0.5〜2質量%、 WO3 0.1〜2質量%、Nb2O5 0.1〜5質量%、 Y2O3 0.1〜3質量%、Gd2O3 0〜1質量%、 Na2O 0〜1質量%、K2O 0〜1質量%、 を含有し、Li 2 Oを含有しないことを特徴とする1.
64〜1.83の屈折率nd及び36〜56のアッベ数
νdを有する無鉛光学ガラス。1. The following composition in the following quantitative ratio on an oxide basis:
Min SiO 2 10 to 25 wt%, B 2 O 3 8~20 wt%, ZrO 2 1 to 5 wt%, TiO 2 1 to 5 wt%, La 2 O 3 10~30 wt%, BaO 30 to 50 weight %, ZnO 0.1 to 2 wt%, CaO 0.5 to 2 wt%, WO 3 0.1 to 2 wt%, Nb 2 O 5 0.1~5 wt%, Y 2 O 3 0.1~ 3 wt%, Gd 2 O 3 0 to 1 wt%, Na 2 O 0 to 1 wt%, K 2 O 0 to 1 wt%, the a free, characterized in that it does not contain Li 2 O 1.
A lead-free optical glass having a refractive index n d of 64-1.83 and an Abbe number v d of 36-56.
分 SiO2 10〜25質量%、B2O3 8〜20質量%、 但し、SiO2+B2O3≧25質量%、 ZrO2 1〜5質量%、TiO2 1〜5質量%、 La2O3 10〜25質量%、BaO 30〜50質量%、 但し、La2O3+BaO≦60質量%、 ZnO 0.1〜2質量%、CaO 0.5〜2質量%、 WO3 0.1〜2質量%、Nb2O5 0.1〜5質量%、 Y2O3 0.1〜3質量%、Gd2O3 0〜1質量%、 Na2O 0〜1質量%、K2O 0〜1質量%、 を含有し、Li 2 Oを含有せず、1.64〜1.75の
屈折率ndを有することを特徴とする請求項1に記載の
無鉛光学ガラス。2. The following composition in the following quantitative ratio on an oxide basis:
Min SiO 2 10 to 25 wt%, B 2 O 3 8 to 20 wt%, however, SiO 2 + B 2 O 3 ≧ 25 wt%, ZrO 2 1 to 5 wt%, TiO 2 1 to 5 wt%, La 2 O 3 10 to 25% by mass, BaO 30 to 50% by mass, provided that La 2 O 3 + BaO ≦ 60% by mass, ZnO 0.1 to 2% by mass, CaO 0.5 to 2% by mass, WO 3 0.1 to 2 mass%, Nb 2 O 5 0.1~5 wt%, Y 2 O 3 0.1~3 wt%, Gd 2 O 3 0~1 wt%, Na 2 O 0~1 wt%, K 2 O 0 to 1 wt%, the has free and does not contain Li 2 O, lead-free optical glass according to claim 1, characterized in that has a refractive index n d of from 1.64 to 1.75.
分 SiO2 10〜17質量%、B2O3 8〜15質量%、 但し、SiO2+B2O3≦25質量%、 ZrO2 1〜5質量%、TiO2 1〜5質量%、 La2O3 15〜30質量%、BaO 30〜50質量%、 但し、La2O3+BaO≧60質量%、 ZnO 0.1〜2質量%、CaO 0.5〜2質量%、 WO3 0.1〜2質量%、Nb2O5 0.1〜5質量%、 Y2O3 0.1〜3質量%、Gd2O3 0〜1質量%、 Na2O 0〜1質量%、K2O 0〜1質量%、 を含有し、Li 2 Oを含有せず、1.75〜1.83の
屈折率ndを有することを特徴とする請求項1に記載の
無鉛光学ガラス。3. The following composition in the following quantitative ratio on an oxide basis:
Min SiO 2 10 to 17 wt%, B 2 O 3 8 to 15 wt%, however, SiO 2 + B 2 O 3 ≦ 25 wt%, ZrO 2 1 to 5 wt%, TiO 2 1 to 5 wt%, La 2 O 3 15 to 30% by mass, BaO 30 to 50% by mass, provided that La 2 O 3 + BaO ≧ 60% by mass, ZnO 0.1 to 2% by mass, CaO 0.5 to 2% by mass, WO 3 0.1 to 2 mass%, Nb 2 O 5 0.1~5 wt%, Y 2 O 3 0.1~3 wt%, Gd 2 O 3 0~1 wt%, Na 2 O 0~1 wt%, K 2 O 0 to 1 wt%, the has free and does not contain Li 2 O, lead-free optical glass according to claim 1, characterized in that has a refractive index n d of from 1.75 to 1.83.
分 SiO2 15〜21質量%、B2O3 10〜15質量%、 ZrO2 1〜4質量%、TiO2 1〜4質量%、 La2O3 15〜25質量%、BaO 30〜43質量%、 ZnO 0.1〜1質量%、CaO 0.5〜1質量%、 但し、BaO+ZnO+CaO≧31質量%、 WO3 0.1〜1質量%、Nb2O5 2〜5質量%、 Y2O3 0.1〜2質量%、Gd2O3 0〜1質量%、 但し、Y2O3+Gd2O3≧0.2質量%、 Na2O 0〜1質量%、K2O 0〜1質量%、 を含有し、Li 2 Oを含有せず、1.71〜1.75の
屈折率nd及び42〜46のアッベ数νdを有することを
特徴とする請求項1に記載の無鉛光学ガラス。4. The following composition in the following quantitative ratio on an oxide basis:
Min SiO 2 15 to 21 wt%, B 2 O 3 10~15 wt%, ZrO 2 1 to 4 wt%, TiO 2 1 to 4 wt%, La 2 O 3 15~25 wt%, BaO 30-43 mass %, ZnO 0.1-1% by mass, CaO 0.5-1% by mass, provided that BaO + ZnO + CaO ≧ 31% by mass, WO 3 0.1-1% by mass, Nb 2 O 5 2-5% by mass, Y 2 O 3 0.1 to 2 % by mass, Gd 2 O 3 0 to 1% by mass, provided that Y 2 O 3 + Gd 2 O 3 ≧ 0.2% by mass, Na 2 O 0 to 1% by mass, K 2 O 0 to 1 wt%, the has free and does not contain Li 2 O, to claim 1, characterized in that it has an Abbe number [nu d of a refractive index n d and 42 to 46 of from 1.71 to 1.75 The lead-free optical glass as described.
aO+ZnO+CaO)≦1であることを特徴とする請
求項4に記載の無鉛光学ガラス。5. A mass ratio of (SiO 2 + B 2 O 3 ) / (B
5. The lead-free optical glass according to claim 4, wherein (aO + ZnO + CaO) ≦ 1.
分 SiO2 15〜17質量%、B2O3 12〜15質量% ZrO2 2〜3質量%、TiO2 2〜3質量%、 La2O3 19〜22質量%、BaO 37〜39質量%、 ZnO 0.1〜1質量%、CaO 0.5〜1質量%、 WO3 0.1〜1質量%、Nb2O5 2〜4質量%、 Y2O3 0.5〜1.5質量%、Gd2O3 0〜1質量%、 但し、Y2O3+Gd2O3≧0.6質量%、 を含有し、Li 2 Oを含有せず、1.73〜1.75の
屈折率nd及び44〜46のアッベ数νdを有することを
特徴とする請求項4に記載の無鉛光学ガラス。6. The following composition in the following quantitative ratio on an oxide basis:
Min SiO 2 15 to 17 wt%, B 2 O 3 12~15 wt% ZrO 2 2 to 3 wt%, TiO 2 2 to 3 wt%, La 2 O 3 19~22 wt%, BaO 37 to 39 wt% , ZnO 0.1 to 1 wt%, CaO 0.5 to 1 wt%, WO 3 0.1 to 1 wt%, Nb 2 O 5 2~4 wt%, Y 2 O 3 0.5~1.5 wt%, Gd 2 O 3 0 to 1 wt%, however, Y 2 O 3 + Gd 2 O 3 ≧ 0.6 wt%, a has free and does not contain Li 2 O, 1.73 to 1.75 The lead-free optical glass according to claim 4, wherein the optical glass has a refractive index n d and an Abbe number v d of 44 to 46.
5質量%であることを特徴とする請求項1乃至6のいず
れか1項に記載の無鉛光学ガラス。7. WO 3 + Nb 2 O 5 + Y 2 O 3 + Gd 2 O 3 ≧
The lead-free optical glass according to any one of claims 1 to 6, wherein the content is 5% by mass.
0であることを特徴とする請求項1乃至7のいずれか1
項に記載の無鉛光学ガラス。8. A mass ratio of ZrO 2 / TiO 2 of 0.8 to 1.
8. The method according to claim 1, wherein the value is 0.
Item 6. The lead-free optical glass according to item 1.
る請求項1乃至8のいずれか1項に記載の無鉛光学ガラThe lead-free optical glass according to claim 1.
ス。Su.
Sb2O3を含有することを特徴とする請求項9に記載の
無鉛光学ガラス。10. The lead-free optical glass according to claim 9 , which contains 0.1 to 0.5% by mass of Sb 2 O 3 as a fining agent .
化物を含有することを特徴とする請求項9に記載の無鉛
光学ガラス。11. The lead-free optical glass according to claim 9 , comprising up to 0.5% by mass of a fluoride as a fining agent .
含有しないことを特徴とする請求項1乃至11のいずれ
か1項に記載の無鉛光学ガラス。12. Except for the unavoidable impurities, lead-free optical glass according to any one of claims 1 to 11, characterized in that do not contain arsenic oxide.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1998148077 DE19848077C1 (en) | 1998-10-19 | 1998-10-19 | Lead-free optical glass |
DE19848077:6 | 1998-10-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2000128568A JP2000128568A (en) | 2000-05-09 |
JP3347106B2 true JP3347106B2 (en) | 2002-11-20 |
Family
ID=7884901
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29477799A Expired - Lifetime JP3347106B2 (en) | 1998-10-19 | 1999-10-18 | Lead-free optical glass |
Country Status (7)
Country | Link |
---|---|
JP (1) | JP3347106B2 (en) |
CN (1) | CN1152836C (en) |
DE (1) | DE19848077C1 (en) |
FR (1) | FR2784676B1 (en) |
GB (1) | GB2342918B (en) |
HK (1) | HK1029098A1 (en) |
MY (1) | MY124408A (en) |
Cited By (1)
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- 1998-10-19 DE DE1998148077 patent/DE19848077C1/en not_active Expired - Lifetime
-
1999
- 1999-09-23 GB GB9922412A patent/GB2342918B/en not_active Expired - Fee Related
- 1999-10-12 FR FR9912705A patent/FR2784676B1/en not_active Expired - Fee Related
- 1999-10-18 MY MYPI9904491 patent/MY124408A/en unknown
- 1999-10-18 JP JP29477799A patent/JP3347106B2/en not_active Expired - Lifetime
- 1999-10-19 CN CNB991251458A patent/CN1152836C/en not_active Expired - Lifetime
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WO2017028725A1 (en) * | 2015-08-14 | 2017-02-23 | 成都光明光电股份有限公司 | Optical glass |
US10442722B2 (en) | 2015-08-14 | 2019-10-15 | Cdgm Glass Co., Ltd | Optical glass |
Also Published As
Publication number | Publication date |
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JP2000128568A (en) | 2000-05-09 |
CN1152836C (en) | 2004-06-09 |
FR2784676A1 (en) | 2000-04-21 |
FR2784676B1 (en) | 2002-07-19 |
GB2342918B (en) | 2001-04-18 |
DE19848077C1 (en) | 2000-01-27 |
GB2342918A (en) | 2000-04-26 |
GB9922412D0 (en) | 1999-11-24 |
CN1252391A (en) | 2000-05-10 |
HK1029098A1 (en) | 2001-03-23 |
MY124408A (en) | 2006-06-30 |
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