JP3347106B2 - Lead-free optical glass - Google Patents

Lead-free optical glass

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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
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JP
Japan
Prior art keywords
mass
lead
optical glass
glass
free
Prior art date
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JP2000128568A (en
Inventor
ウヴェ、コルベルク
グラボウスキー ダヌータ
マグダレナ、ヴィンクレル−トゥルーデヴィッヒ
ヴォルフ ジルケ
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カール−ツァイス−スティフツング
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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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  • 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

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【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)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 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。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. 【請求項２】 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％、 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. 【請求項３】 酸化物基準で以下の量的割合で以下の成
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. 【請求項４】 酸化物基準で以下の量的割合で以下の成
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. 【請求項５】 質量比で（ＳｉＯ2＋Ｂ2Ｏ3）／（Ｂ
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. 【請求項６】 酸化物基準で以下の量的割合で以下の成
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. 【請求項７】 ＷＯ3＋Ｎｂ2Ｏ5＋Ｙ2Ｏ3＋Ｇｄ2Ｏ3≧
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. 【請求項８】 質量比ＺｒＯ2／ＴｉＯ2が０．８〜１．
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. 【請求項９】 さらに清澄剤を含有することを特徴とす9. The method according to claim 6, further comprising a fining agent.
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. 【請求項１０】 清澄剤として０．１〜０．５質量％の
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 . 【請求項１１】 清澄剤として０．５質量％までのフッ
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 . 【請求項１２】 不可避的な不純物を除き、酸化ヒ素を
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.
JP29477799A 1998-10-19 1999-10-18 Lead-free optical glass Expired - Lifetime JP3347106B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19848077:6 1998-10-19
DE1998148077 DE19848077C1 (en) 1998-10-19 1998-10-19 Lead-free optical glass

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JP2000128568A JP2000128568A (en) 2000-05-09
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DE (1) DE19848077C1 (en)
FR (1) FR2784676B1 (en)
GB (1) GB2342918B (en)
HK (1) HK1029098A1 (en)
MY (1) MY124408A (en)

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JP2000128568A (en) 2000-05-09
GB2342918A (en) 2000-04-26
FR2784676A1 (en) 2000-04-21
DE19848077C1 (en) 2000-01-27
HK1029098A1 (en) 2001-03-23
GB9922412D0 (en) 1999-11-24
CN1152836C (en) 2004-06-09
GB2342918B (en) 2001-04-18
CN1252391A (en) 2000-05-10
FR2784676B1 (en) 2002-07-19

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