JP2528419B2 - Optical phosphate glasses exhibiting anomalous partial dispersion in the blue region - Google Patents
Optical phosphate glasses exhibiting anomalous partial dispersion in the blue regionInfo
- Publication number
- JP2528419B2 JP2528419B2 JP4190238A JP19023892A JP2528419B2 JP 2528419 B2 JP2528419 B2 JP 2528419B2 JP 4190238 A JP4190238 A JP 4190238A JP 19023892 A JP19023892 A JP 19023892A JP 2528419 B2 JP2528419 B2 JP 2528419B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- weight
- partial dispersion
- blue region
- anomalous partial
- 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.)
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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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
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]
【産業上の利用分野】本発明は、スペクトルの青色領域
で正の異常部分分散を示し、屈折率nd >1.57,ア
ッベ数νd >64で、結晶化安定性及び透過性に優れた
光学燐酸塩ガラスに関する。The present invention shows a positive anomalous partial dispersion in the blue region of the spectrum, a refractive index n d > 1.57, an Abbe number ν d > 64 and excellent crystallization stability and transparency. Optical phosphate glass.
【0002】[0002]
【従来の技術と発明が解決しようとする課題】異常部分
分散を示すガラスは、いわゆる二次スペクトルの補正の
ために使用される。その場合、正常直線からの特に高い
偏りを示すガラスが好んで用いられる。スペクトルの青
色領域での部分分散能は、下記化1の式で示される。Glass exhibiting anomalous partial dispersion is used for the correction of so-called secondary spectra. In that case, glass showing a particularly high deviation from the normal line is preferably used. The partial dispersion power in the blue region of the spectrum is shown by the following chemical formula 1.
【化1】 ここで、ng は波長435.83nmでの屈折率、nF'
は479.99nmでの屈折率、nC'は643.85n
mでの屈折率を表す。Embedded image Here, n g is the refractive index at a wavelength of 435.83 nm, and n F ′
Refractive index at 479.99nm is, n C 'is 643.85n
Represents the refractive index at m.
【0003】多数のガラス、いわゆる普通ガラスは下記
化2の一次関係式を近似的に満足する。A large number of glasses, so-called ordinary glasses, approximately satisfy the linear relational expression below.
【化2】PX,Y =AX,Y +BX,Y ・νd [Formula 2] P X, Y = A X, Y + B X, Y · ν d
【0004】ガラスK7及びF2(1980年独マイン
ツのショット・グラスヴェルケ社(Schott Gl
aswerke)発行のショット−カタログ「光学ガラ
ス」参照)については、部分分散能を示す直線、即ち標
準直線は、スペクトルの青色領域では下記化3の式で示
される。Glasses K7 and F2 (Schott Gl (Schott Gl), Mainz, Germany, 1980
As for the shot published by Aswerke-see catalog "Optical glass"), a straight line showing the partial dispersion power, that is, a standard straight line is represented by the following formula 3 in the blue region of the spectrum.
【化3】 P'g,F' =0.5671−0.001422・νe Embedded image P ′ g, F ′ = 0.5671-0.001422 · ν e
【0005】ここで、νe は下記化4の式で示される。Here, ν e is expressed by the following equation (4).
【化4】 (ne は波長546.07nmでの屈折率) 上記化3の曲線から偏るガラスは異常部分分散を有す
る。偏りの尺度として、或る点における標準直線に対し
て変位した座標差△P'g,F' が用いられる。この値が△
P'g,F' >0であれば、このガラスを正偏差部分分散ガ
ラスと呼ぶ。Embedded image (N e is a refractive index at a wavelength of 546.07 nm) Glass deviating from the curve of the above chemical formula 3 has anomalous partial dispersion. The coordinate difference ΔP ′ g, F ′ displaced with respect to the standard line at a certain point is used as a measure of the bias. This value is △
If P'g, F ' > 0, this glass is called positive deviation partial dispersion glass.
【0006】本発明の課題は、屈折率nd が1,57を
越え、アッベ数νd が64を越える光学燐酸塩ガラスを
見出すことである。また、このガラスは高い耐失透性と
良好な透過能を特徴とし、簡単かつ安価に製造すること
ができなければならない。An object of the present invention is to find an optical phosphate glass having a refractive index n d of more than 1,57 and an Abbe number ν d of more than 64. The glass must also be characterized by high resistance to devitrification and good permeability and be able to be manufactured easily and inexpensively.
【0007】既に多数の光学燐酸塩ガラスが知られてい
るが、上記の要求に全ゆる点で適合するガラスは未だに
開発されていない。ドイツ特許出願公告第1 089
935号には、少なくとも4重量%のZnO又はCdO
を含むガラスが開示されている。労働衛生上の理由から
CdOの使用は回避されている。ZnO含有ガラスはア
ルカリ性溶液にひどく侵食されるので(A.M.スムー
ト(A.M.Smoot)「英国採鉱雑誌Eng.Mi
ning J.」91(1911年)1098頁、Z.
ガロッツィ(Z.Garozzi)「工業応用科学雑誌
Giornale di chimica ind.e
d appl.」7(1925年)129頁を参照)、
ZnO含量の増加につれてアルカリに対する耐薬品性が
減少する。ドイツ特許出願公告第23 42 484号
及びドイツ特許出願公開第3634 675A1号に
は、本発明に係るガラスより高いAl2 O3 含量と低い
P2 O5 含量を含むガラスが記載されている。このた
め、これらのガラスの失透しやすさが増加している。Although a large number of optical phosphate glasses are already known, a glass which meets all the above requirements in all respects has not yet been developed. German Patent Application Publication No. 1089
935, at least 4% by weight ZnO or CdO
A glass containing is disclosed. The use of CdO is avoided for reasons of occupational health. Since ZnO-containing glasses are severely eroded by alkaline solutions (AM Smoot, Eng. Mi, UK Mining Magazine).
Ning J. 91 (1911) 1098, Z.
Z. Garozzi "Industrial Applied Science Journal Giornale di chimica ind.e.
d appl. 7 (1925, p. 129),
Chemical resistance to alkali decreases with increasing ZnO content. DE-A 23 42 484 and DE-A 3634 675 A1 describe glasses with a higher Al 2 O 3 content and a lower P 2 O 5 content than the glasses according to the invention. Therefore, devitrification of these glasses is increasing.
【0008】特開昭50−8447号公報に記載された
ガラスは、短波長域で異常部分分散を得るために、最小
含量のTiO2 を含んでいる。紫外領域で強く吸収する
Ti3+イオン分が溶融時にほぼ必然的に得られるので、
このガラスは紫外線透過性が最適でない。特開昭52−
68217号公報に記載のガラスは、僅かな添加量の高
価な元素ランタン、ガドリニウム、イッテルビウム又は
イットリウムの酸化物を含んでおり、アッベ数が64未
満で色収差が低い。The glass described in JP-A-50-8447 contains a minimum content of TiO 2 in order to obtain anomalous partial dispersion in the short wavelength region. Since Ti 3+ ions that strongly absorb in the ultraviolet region are almost inevitably obtained during melting,
This glass is not optimally UV transparent. JP-A-52-
The glass described in Japanese Patent No. 68217 contains a small amount of an expensive oxide of lanthanum, gadolinium, ytterbium or yttrium, and has an Abbe number of less than 64 and low chromatic aberration.
【0009】本発明は、前記したように、屈折率nd が
1.57を越え、かつアッベ数νdが64を越えるこ
と、また高い耐失透性と良好な透過能を有すること、さ
らに簡単にかつ安価に製造できることの全ての要求を満
足し得る、スペクトルの青色領域で正の異常部分分散を
示す光学燐酸塩ガラスを提供しようとするものである。The present invention, as described above, has a refractive index n d of more than 1.57 and an Abbe number ν d of more than 64, and has high devitrification resistance and good transparency. The aim is to provide an optical phosphate glass exhibiting a positive anomalous partial dispersion in the blue region of the spectrum which can satisfy all the requirements of being easy and inexpensive to manufacture.
【0010】[0010]
【課題を解決するための手段】上記課題は請求項1に記
載したガラスによって解決される。本発明の光学燐酸塩
ガラスは、酸化物ベースでSiO2 :0〜2重量%、A
l2 O3 :0〜3重量%、Li2 O:0〜2重量%、N
a2 O:0〜2重量%、K2 O:0〜2重量%、Σアル
カリ酸化物:0〜2重量%、MgO:2〜6重量%、C
aO:0〜8.5重量%、SrO:0〜8重量%、Ba
O:32〜51重量%、ZnO:0〜1重量%、ΣRO
(=MgO+CaO+SrO+BaO+ZnO):46
〜56重量%、La2 O3 :0〜2重量%、Ta2 O
5 :0〜2重量%、WO3 :0〜2重量%、ZrO2 :
0〜2重量%、P2 O5 :38〜49重量%、F:0〜
3.5重量%、F2-O:0〜2重量%を含み、ΣRO/
P2 O5 の比が1〜1.4の範囲に規定される。F2-O
は、2価酸素イオンを2個の1価フッ化物イオンで置換
することにより生じる成分を表す。The above problems are solved by the glass according to claim 1. The optical phosphate glass of the present invention has an oxide base of SiO 2 : 0 to 2 wt%, A
l 2 O 3 : 0 to 3% by weight, Li 2 O: 0 to 2% by weight, N
a 2 O: 0 to 2% by weight, K 2 O: 0 to 2% by weight, Σ alkali oxide: 0 to 2% by weight, MgO: 2 to 6% by weight, C
aO: 0 to 8.5% by weight, SrO: 0 to 8% by weight, Ba
O: 32 to 51% by weight, ZnO: 0 to 1% by weight, ΣRO
(= MgO + CaO + SrO + BaO + ZnO): 46
To 56 wt%, La 2 O 3: 0~2 wt%, Ta 2 O
5: 0-2 wt%, WO 3: 0 to 2 wt%, ZrO 2:
0-2 wt%, P 2 O 5: 38~49 wt%, F: 0 to
3.5% by weight, F 2 -O: 0 to 2% by weight, ΣRO /
The ratio of P 2 O 5 is specified in the range of 1 to 1.4. F 2 -O
Represents a component generated by replacing a divalent oxygen ion with two monovalent fluoride ions.
【0011】[0011]
【発明の作用及び態様】本発明は、ガラス系においてP
2 O5 、BaO、MgOが前記範囲内に規制されること
により、紫外領域の透過が高く、しかもスペクトルの青
色領域で高い正異常部分分散を示す特に安定なガラスを
得ることができるという知見に基づいている。2価酸化
物RO(=MgO+CaO+SrO+BaO+ZnO)
の含量の和とP2 O5 含量の比が1〜1.4であれば、
このガラス系にガラス成分CaO、SrO及びZnOを
加えることができる。この比は、少ない失透傾向と高い
耐薬品性の要求の折衷である。この比を下回れば、耐薬
品性に対するP2 O5 成分の否定的影響が増し、耐薬品
性が明らかに低いガラスが得られる。一方、RO/P2
O5 比が1.4を越えると、2価ガラス成分の否定的影
響が現れ、このガラスは著しく高い失透傾向を有するこ
とになる。The function and mode of the present invention are as follows.
It has been found that by controlling 2 O 5 , BaO, and MgO within the above range, it is possible to obtain a particularly stable glass that has a high transmission in the ultraviolet region and has a high anomalous partial dispersion in the blue region of the spectrum. Is based. Divalent oxide RO (= MgO + CaO + SrO + BaO + ZnO)
If the ratio of the sum of the contents of P 2 O 5 and the content of P 2 O 5 is 1 to 1.4,
The glass components CaO, SrO and ZnO can be added to this glass system. This ratio is a compromise between low devitrification tendency and high chemical resistance requirements. Below this ratio, the negative influence of the P 2 O 5 component on the chemical resistance increases, and a glass having a clearly low chemical resistance is obtained. On the other hand, RO / P 2
If the O 5 ratio exceeds 1.4, the negative effect of the divalent glass component appears, and this glass has a remarkably high devitrification tendency.
【0012】ガラス系にアルカリ酸化物(Li2 O、N
a2 O、K2 O、Rb2 O、Cs2O)を合計2重量%
まで加えても、それによってガラス系の耐凝離性は損な
われない。しかし、アルカリ酸化物の添加は行わないこ
とが好ましい。また屈折率を高めるために、高屈折力成
分、例えばLa2 O3 、WO3 、Ta2 O5 等を加える
ことができる。但し、紫外領域の透過に対する否定的影
響が増大する恐れがあるので、これらの成分の総含量を
なるべく低くしなければならない。また、高屈折力成分
の添加は融解温度を高めるから、溶解槽に対する溶融物
の侵食が増加することとなり、それがガラスの品質に対
して否定的影響を及ぼす。従って、やはり上記の添加物
の添加を行わないことが好ましい。Alkali oxides (Li 2 O, N
a 2 O, K 2 O, Rb 2 O, Cs 2 O) in total of 2% by weight
However, it does not impair the segregation resistance of the glass system. However, it is preferable not to add an alkali oxide. Further, in order to increase the refractive index, a high refractive power component such as La 2 O 3 , WO 3 or Ta 2 O 5 can be added. However, since the negative influence on the transmission in the ultraviolet region may increase, the total content of these components should be as low as possible. Also, the addition of the high refractive power component raises the melting temperature, which leads to an increase in the erosion of the melt to the melting tank, which negatively affects the quality of the glass. Therefore, it is preferable not to add the above additives.
【0013】フッ化物イオンの含量は3.5重量%以
下、又はフッ素による酸素イオンの置換の結果生じる重
量増加として計算して2重量%以下である。しかし、高
いフッ化物イオン添加量によりガラスの失透挙動が著し
く変化し、このためガラスの生産性が著しく悪化するこ
とがあるから、フッ化物イオン含量はなるべく少なく
し、むしろ全く存在しないようにすることが好ましい。The content of fluoride ions is less than 3.5% by weight, or less than 2% by weight, calculated as the weight increase resulting from the displacement of oxygen ions by fluorine. However, since the devitrification behavior of glass may be significantly changed by the high addition amount of fluoride ions, and thus the productivity of glass may be significantly deteriorated, the fluoride ion content should be as low as possible, and rather should not be present at all. It is preferable.
【0014】ガラスは主として2価酸化物とP2 O5 か
ら成る。その場合、ガラスは2〜6重量%のMgO、0
〜8.5重量%のCaO、0〜8重量%のSrO、32
〜51重量%のBaO、0〜1重量%のZnOを含まな
ければならない。但し、CaO及びSrO含量は、上記
の範囲の下限、即ち0〜2重量%又は0〜3重量%であ
ることが好ましい。BaO含量については45〜51重
量%であれば有利であることが判明した。P2 O5 の重
量比は38〜49重量%でなければならず、P2 O5 の
重量比が44〜49重量%であることが好ましい。フッ
化物イオン含量は、前述のようになるべく低くなければ
ならず、0であることが好ましいが、0.6重量%又は
F2-Oとして計算して0.5重量%以下の含量でも好結
果が得られる。Glass mainly consists of divalent oxides and P 2 O 5 . In that case, the glass is 2-6 wt% MgO, 0
~ 8.5 wt% CaO, 0-8 wt% SrO, 32
˜51 wt% BaO, 0-1 wt% ZnO must be included. However, the CaO and SrO contents are preferably the lower limit of the above range, that is, 0 to 2% by weight or 0 to 3% by weight. It has been found to be advantageous for the BaO content to be between 45 and 51% by weight. The weight ratio of P 2 O 5 should be 38-49% by weight, preferably the weight ratio of P 2 O 5 is 44-49% by weight. The fluoride ion content should be as low as possible as described above, and is preferably 0, but a content of 0.5% by weight or less calculated as 0.6% by weight or F 2 -O is also satisfactory. Is obtained.
【0015】必要ならば、ガラスは更に従来公知の清澄
剤を含むことができる。その場合、通常As2 O3 、S
b2 O3 、硝酸塩及び硫酸塩のような清澄剤、場合によ
ってはCeO2 を使用することができる。但し、ガラス
に残留する清澄剤の割合は一般に0.5重量%を越えて
はならない。この程度の量の清澄剤は、正異常部分分散
に対してあまり影響しない。If desired, the glass may additionally contain conventionally known fining agents. In that case, usually As 2 O 3 , S
Fining agents such as b 2 O 3 , nitrates and sulphates and optionally CeO 2 can be used. However, the proportion of fining agent remaining in the glass should generally not exceed 0.5% by weight. This amount of fining agent has little effect on the anomalous partial dispersion.
【0016】[0016]
【実施例】以下、実施例を示して本発明の効果について
具体的に示すが、本発明が下記実施例に限定されるもの
でないことはもとよりである。正確に計量した重量比の
慣用のガラス原料(酸化物、燐酸塩、炭酸塩等)で良好
な配合物を調合した。配合物を1100℃で融解し、次
に清澄及び均質化した。完成ガラスを予熱した鋳型に約
900℃で注入した。例として溶解した5種のガラスの
組成と性質を表1に示す。EXAMPLES Hereinafter, the effects of the present invention will be specifically shown by showing Examples, but it goes without saying that the present invention is not limited to the following Examples. Good formulations were prepared with precisely weighed weight ratios of conventional glass raw materials (oxides, phosphates, carbonates, etc.). The formulation was melted at 1100 ° C, then clarified and homogenized. The finished glass was poured into a preheated mold at about 900 ° C. Table 1 shows the compositions and properties of five types of glass melted as examples.
【表1】 [Table 1]
【0017】[0017]
【発明の効果】上記表1に示す結果からも明らかなよう
に、本発明の光学燐酸塩ガラスは、スペクトルの青色領
域で正異常部分分散を示し、屈折率nd >1.57、ア
ッベ数νd >64であり、かつ結晶化安定性及び透過性
に優れている。また、本発明の光学燐酸塩ガラスの特別
の利点は、その製造が特別の燐酸塩原料に縛られない
で、任意の原料の組合わせにより必要な燐酸塩分を導入
することができることである。このため、ガラスの工業
生産において使用原料の融通性によって大きな利益が生
じる。As is clear from the results shown in Table 1 above, the optical phosphate glass of the present invention exhibits a positive anomalous partial dispersion in the blue region of the spectrum, a refractive index n d > 1.57, and an Abbe number. ν d > 64 and excellent in crystallization stability and permeability. Also, a particular advantage of the optical phosphate glass of the present invention is that its production is not tied to a particular phosphate raw material and the required phosphate content can be introduced by any combination of raw materials. For this reason, in the industrial production of glass, the flexibility of raw materials used brings great benefits.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 フォルクマール、ゲイラー ドイツ連邦共和国、6500 マインツ、ゼ ルトリウスリング 239 (56)参考文献 特開 昭48−21708(JP,A) 特公 昭50−8447(JP,B2) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Volkmar, Gailler, Federal Republic of Germany, 6500 Mainz, Zeltorius Ring 239 (56) Reference JP-A-48-21708 (JP, A) JP-B-50-8447 (JP, B2)
Claims (2)
/P2 O5 の比が1〜1.4であり、スペクトルの青色
領域で正異常部分分散を示し、屈折率nd >1.57,
アッベ数νd >64で、結晶化安定性及び透過性に優れ
た光学燐酸塩ガラス。1. The following composition: MgO 2 to 6 wt%, SiO 2 0 to 2 wt%, CaO 0 to 8.5 〃, Al 2 O 3 0 to 3 〃, SrO 0 to 8 〃, Li 2 O 0 ˜2 〃, BaO 32 to 51 〃, Na 2 O 0 to 2 〃, ZnO 0-1 〃, K 2 O 0 to 2 〃, ΣRO 46 to 56 〃, ∑ alkali oxide 0 to 2 〃, (RO = ZnO + MgO + CaO + SrO + BaO) P 2 O 5 38 to 49 〃, La 2 O 3 0 to 2 〃, Ta 2 O 5 0 to 2 〃, F 0 to 3.5 〃, WO 3 0 to 2 〃, F 2 -O 0 〜 2 〃, ZrO 2 0 to 2 〃, optionally containing a conventional fining agent, and ΣRO
The ratio of / P 2 O 5 is 1 to 1.4, it shows a positive anomalous partial dispersion in the blue region of the spectrum, and the refractive index n d > 1.57
An optical phosphate glass with an Abbe number ν d > 64 and excellent crystallization stability and transparency.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4128676.6 | 1991-08-29 | ||
DE19914128676 DE4128676C1 (en) | 1991-08-29 | 1991-08-29 | Optical phosphate glass with high refractive index and Abbe number - comprises oxide(s) of magnesium, calcium, strontium, barium, zinc and phosphorus, and fluoride |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07196336A JPH07196336A (en) | 1995-08-01 |
JP2528419B2 true JP2528419B2 (en) | 1996-08-28 |
Family
ID=6439395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4190238A Expired - Fee Related JP2528419B2 (en) | 1991-08-29 | 1992-06-25 | Optical phosphate glasses exhibiting anomalous partial dispersion in the blue region |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP2528419B2 (en) |
DE (1) | DE4128676C1 (en) |
FR (1) | FR2680779B1 (en) |
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JP3321414B2 (en) * | 1997-06-17 | 2002-09-03 | ホーヤ株式会社 | Light polarization control element |
JP4162532B2 (en) * | 2003-04-18 | 2008-10-08 | Hoya株式会社 | Optical glass, press-molding preform and manufacturing method thereof, optical element and manufacturing method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE634699C (en) * | 1933-02-23 | |||
FR1074685A (en) * | 1952-02-26 | 1954-10-07 | Leitz Ernst Gmbh | Optical glass |
DE1293400B (en) * | 1962-06-05 | 1969-04-24 | Jenaer Glaswerk Schott & Gen | Process for making an optical glass |
GB1174475A (en) * | 1967-06-22 | 1969-12-17 | English Electric Co Ltd | Glass-Ceramics. |
JPS508447B1 (en) * | 1970-03-02 | 1975-04-04 |
-
1991
- 1991-08-29 DE DE19914128676 patent/DE4128676C1/en not_active Expired - Fee Related
-
1992
- 1992-06-25 JP JP4190238A patent/JP2528419B2/en not_active Expired - Fee Related
- 1992-08-04 FR FR9209648A patent/FR2680779B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH07196336A (en) | 1995-08-01 |
DE4128676C1 (en) | 1993-03-04 |
FR2680779B1 (en) | 1995-03-17 |
FR2680779A1 (en) | 1993-03-05 |
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