JPS6212633A - Glass composition suitable for producing transparent material of refractive index distribution type - Google Patents

Glass composition suitable for producing transparent material of refractive index distribution type

Info

Publication number
JPS6212633A
JPS6212633A JP14684985A JP14684985A JPS6212633A JP S6212633 A JPS6212633 A JP S6212633A JP 14684985 A JP14684985 A JP 14684985A JP 14684985 A JP14684985 A JP 14684985A JP S6212633 A JPS6212633 A JP S6212633A
Authority
JP
Japan
Prior art keywords
0mol
refractive index
glass
glass composition
index distribution
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.)
Pending
Application number
JP14684985A
Other languages
Japanese (ja)
Inventor
Yoshitaka Yoneda
嘉隆 米田
Yoshiyuki Asahara
浅原 慶之
Shigeaki Omi
成明 近江
Hiroyuki Sakai
裕之 坂井
Shin Nakayama
伸 中山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoya Corp
Original Assignee
Hoya Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoya Corp filed Critical Hoya Corp
Priority to JP14684985A priority Critical patent/JPS6212633A/en
Publication of JPS6212633A publication Critical patent/JPS6212633A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight

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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)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

PURPOSE:To form a glass composition capable of producing a lens of cesium- containing refractive index distribution type having high numerical aperture, which can be produced from an existing glass composition, by ion exchange method, by adding zinc and optionally other bivalent ions to parent material glass. CONSTITUTION:A glass composition suitable for producing a transparent material of refractive index distribution type comprising 30-75mol% SiO2, 2-25mol% Cs2O and 2-40mol% ZnO as essential components and 15-0mol% Na2O, 15-0mol% Li2O, 15-0mol% K2O, 15-0mol% B2O3, 15-0mol% Al2O3, 15-0mol% TiO2, 7-0mol% ZrO2, 5-0mol% Ta2O5, 7-0mol% Nb2O3, 5-0mol% WO3, 15-0mol% La2O3+Y2O3, 25-0mol% CaO, 25-0mol% MgO, 25-0mol% SrO, 25-0mol% BaO, 25-0mol% PbO and 0.5-0mol% As2O3+Sb2O3 as arbitrary components.

Description

【発明の詳細な説明】 本発明は、ガラス中のセシウムイオンを伯のアルカリイ
オンとイオン交換することによって高量【」数を有する
屈折率分布型レンズを製造するのに適したガラス組成物
に関づる。
DETAILED DESCRIPTION OF THE INVENTION The present invention provides a glass composition suitable for producing a gradient index lens having a high number of cesium ions by ion-exchanging cesium ions in the glass with alkali ions. Related.

ガラスを溶WA塩中に浸漬してガラスに含まれるアルカ
リイオンX+を溶融塩中の他のアルカリイオンX2と連
続的に交換させることにより、X+イオンの濃度がガラ
スの中心軸から周辺にかけて次第に減少する放物線状の
屈折率勾配を形成させるイオン交換法は、屈折率分布型
レンズの製造法として人聞生産性および再現性に優れて
いることから、最も一般的に用いられている。
By immersing the glass in molten WA salt and continuously exchanging the alkali ions X+ contained in the glass with other alkali ions X2 in the molten salt, the concentration of X+ ions gradually decreases from the central axis of the glass to the periphery. The ion exchange method, which forms a parabolic refractive index gradient, is the most commonly used method for producing gradient index lenses because it has excellent human productivity and reproducibility.

ガラス中に含まれるX1イオン、すなわちドーパントイ
オンとしては、電子分極率の高いもの(TIl÷、C8
+、Rb÷など)と、他のイオンを分極させる能力の大
きいもの(Li+)が挙げられる。Tf”をドーパント
として用いた場合は、電子分極率が高いためガラス中心
軸と周辺部との屈折率差が大きく、開口数の高いレンズ
が作製できるが、ガラス溶解時にTfが揮発し、人体に
多大な書を及ぼす危険がある。これに加えて、T2含有
ガラスは屈折率の波長分散が大きく色収差が大であり、
白色光を光源としたとき解像力が大きく低下するという
欠点もある。
The X1 ions contained in the glass, that is, the dopant ions, have a high electronic polarizability (TIl÷, C8
+, Rb÷, etc.) and those with a large ability to polarize other ions (Li+). When Tf'' is used as a dopant, the difference in refractive index between the central axis of the glass and the periphery is large due to its high electronic polarizability, and a lens with a high numerical aperture can be manufactured. In addition, T2-containing glass has large wavelength dispersion of refractive index and large chromatic aberration.
Another drawback is that the resolution is greatly reduced when white light is used as a light source.

またLi+をドーパントにした場合は、これと置換する
イオンがli+より大ぎなイオンであるので、ガラス中
に内部歪が残留し、イオン交換後割れが発生しやすいの
で、屈折率差の大きなレンズを作製できない不都合があ
る。
In addition, when Li+ is used as a dopant, the ions that replace it are larger than Li+, so internal strain remains in the glass and cracks are likely to occur after ion exchange, so lenses with a large refractive index difference are used. There is an inconvenience that it cannot be manufactured.

こうした理由からC8+をドーパントにして、色収差が
小さく屈折率差の大きな屈折率分布型レンズが待望され
ている。しかしながら、C5+をドーパントイオンとし
てイオン交換法でレンズを作製すると (1)電子分極率がTf+より低く、ガラスの中心軸と
周辺で大きな屈折率差を形成できない (2拡散速瓜が遅く、長いイオン交換時間を必要として
生産性が悪い c3+屈折率差を大きくするためにCs1fiを増加さ
せるとC52025モル%以上ではガラスの耐候性が著
しく悪くなり、実用に適さなくなる などのさまざまな弊害がある。このため、従来のセシウ
ム含有屈折率分布型レンズは、せいぜい開口数が061
程度のものが生産されているにすぎない。
For these reasons, there has been a long-awaited demand for a gradient index lens that uses C8+ as a dopant and has small chromatic aberration and a large difference in refractive index. However, when a lens is made by the ion exchange method using C5+ as a dopant ion, (1) the electronic polarizability is lower than that of Tf+, and a large refractive index difference cannot be formed between the central axis and the periphery of the glass (2) the diffusion rate is slow, and long ion If Cs1fi is increased in order to increase the C3+ refractive index difference, which requires replacement time and reduces productivity, if C5202025 mol% or more, the weather resistance of the glass deteriorates significantly, causing various problems such as making it unsuitable for practical use. Therefore, conventional cesium-containing gradient index lenses have a numerical aperture of 0.61 at most.
Only a limited amount is produced.

本発明は亜鉛と必要に応じて他の2(iiイオンを母材
ガラス中に含有させることによって、従来のガラス組成
では得ることのできなかった高開口数のセシウム含有屈
折率分布型レンズをイオン交換法で製造することができ
るガラス組成物を提供するものである。
By incorporating zinc and, if necessary, other 2 (II) ions into the base glass, the present invention can produce a cesium-containing graded index lens with a high numerical aperture that could not be obtained with conventional glass compositions. The present invention provides a glass composition that can be produced by an exchange method.

すなわち、高開口数を有するセシウム含有屈折率分布型
レンズの製造に適した本発明のガラスは、モル%で30
〜75Si02.2〜25C820及び2〜40ZnO
を必須成分と含有し、任意成分として0〜15Na20
、O〜151 i20,0〜15に20.0〜15B2
0z 、0〜15Aj2203 、O〜15「102.
0〜7ZrO2,0〜5Ta205、O〜7Nb203
 、O〜5WO3、O〜15(L a 203+Y2O
3)、0〜2508010〜25Mg010〜25Sr
O10〜25Bao10〜25PbO10〜0.5(A
S203 +Sbz 03 )を含有する。
That is, the glass of the present invention suitable for manufacturing a cesium-containing gradient index lens having a high numerical aperture has a mol% of 30
~75Si02.2~25C820 and 2~40ZnO
Contains 0 to 15 Na20 as an essential component, and 0 to 15 Na20 as an optional component.
, O~151 i20, 0~15 to 20.0~15B2
0z, 0~15Aj2203, O~15"102.
0~7ZrO2, 0~5Ta205, O~7Nb203
, O~5WO3, O~15 (L a 203+Y2O
3), 0~2508010~25Mg010~25Sr
O10~25Bao10~25PbO10~0.5(A
S203 +Sbz 03 ).

次にガラス組成限定範囲の詳細な説明を行う。Next, the glass composition limited range will be explained in detail.

まず5iOzはガラスの耐候性の面から30モル%以上
必要であるが、75モル%を越えるとガラスの溶解温度
が高くなり過ぎ、実用、ヒ不適当である。
First, 5iOz is required in an amount of 30 mol % or more from the viewpoint of the weather resistance of the glass, but if it exceeds 75 mol %, the melting temperature of the glass becomes too high, making it inappropriate for practical use.

またドーパントC920を高濃度で含有させる意味でも
15モル%以下が好ましい。
Also, it is preferably 15 mol % or less in order to contain the dopant C920 at a high concentration.

ドーパントのC820(1が2モル%未満ではイオン交
換法で形成される屈折率差が小さ過ぎてレンズとしての
効果が期待できない。C320filを多くするにつれ
、屈折率差を大きくすることができるが、25モル%を
越えるとガラスの耐候性が著しく悪化するので不適当で
ある。ZnOは第1表に示すとおり、特に屈折率差を大
きくする効果とイオン交換速度を早くする効果を持って
いるので、本発明では2〜40モル%の範囲を可とする
If the dopant C820 (1) is less than 2 mol %, the refractive index difference formed by the ion exchange method is too small and the effect as a lens cannot be expected.As the amount of C320fil increases, the refractive index difference can be increased. If it exceeds 25 mol%, it is unsuitable because the weather resistance of the glass will deteriorate significantly.As shown in Table 1, ZnO has the effect of particularly increasing the refractive index difference and increasing the ion exchange rate. In the present invention, a range of 2 to 40 mol% is allowed.

NazOはガラスの溶解温度を適当な温度域に設定する
ため、アルカリ総量(C520+Na2O+に20+L
 iz O)を15〜30モル%に調節する目的で加え
る。その他にガラス溶解湿度を下げる目的で8203 
、Li2O,に20をそれぞれ0〜15モル%の範囲で
、またガラスの化学的耐久性を向上させる目的でAj2
20x 、TfOz 、Zr’02 、Ta205 、
Nb2O2、La20:l 。
For NazO, in order to set the melting temperature of glass in an appropriate temperature range, the total amount of alkali (20 + L to C520 + Na2O +
iz O) is added for the purpose of adjusting the content to 15 to 30 mol%. In addition, 8203 is used for the purpose of lowering glass melting humidity.
, Li2O, and 20 in the range of 0 to 15 mol%, and Aj2 for the purpose of improving the chemical durability of the glass.
20x, TfOz, Zr'02, Ta205,
Nb2O2, La20:l.

Y203 、CablMQO,SrO,BadlPbO
をそれぞれ上記の範囲で含むことができ、さらに清澄剤
としてAszO3及び/又は5bzO3を0〜0.5モ
ル%の範囲で含むことができる。
Y203, CablMQO, SrO, BadlPbO
can be contained in the above-mentioned ranges, and further AszO3 and/or 5bzO3 can be contained as a refining agent in the range of 0 to 0.5 mol%.

上記の如き本発明のガラス組成物は、これを円柱状、板
状又は球状のガラス体に成型し、常法通りこれにイオン
交換法を適用すれば、近似的に次式で示されるような放
射線状の屈折率分布を有する高開口数の集光性レンズを
製造することができる。
The glass composition of the present invention as described above can be formed into a cylindrical, plate-like or spherical glass body, and if an ion exchange method is applied to the glass body in a conventional manner, the glass composition of the present invention can be obtained approximately as shown by the following formula. A high numerical aperture condensing lens having a radial refractive index distribution can be manufactured.

n (r)2 =no2 (1−g2r2)ここで、n
(r):光軸に垂直な面内で光軸からの距離rでの屈折
率 no  :中心軸での屈折率 q  :正の常数 以下実施例について述べる。
n (r)2 = no2 (1-g2r2) where, n
(r): refractive index at a distance r from the optical axis in a plane perpendicular to the optical axis no: refractive index at the central axis q: positive constant Below Examples will be described.

実施例1 ガラスが10kg程度得られるように原料を秤量、混合
し、白金るつぼを用いて1300℃で10時間、泡脈理
の発生を防ぎながら溶融した後、金型に流し出して成型
、徐冷した。徐冷終了後、15s+iφの丸棒に加工し
、この丸棒を硝酸カリウム溶融塩中に各ガラスの屈伏点
付近の温度で所定時間浸漬してイオン交換した後、所定
の長さに切断し、その両端面をrtll P、してレン
ズとした。ガラス組成を種々変えて作製した各レンズの
中心部での屈折率(no)、中心部と周辺部との屈折率
差(Δn)、レンズの開口数(N、A、)と屈折率分布
が理想的な分布になるまでに要するイオン交換時間(1
゜E、)を第1表及び第2表に示す。
Example 1 Raw materials were weighed and mixed to obtain about 10 kg of glass, melted in a platinum crucible at 1300°C for 10 hours while preventing the generation of bubble striae, and then poured into a mold, molded, and slowly melted. It got cold. After slow cooling, it is processed into a round bar of 15s + iφ, and this round bar is immersed in molten potassium nitrate at a temperature near the yield point of each glass for a predetermined period of time for ion exchange, and then cut into a predetermined length. Both end surfaces were rtll P to form a lens. The refractive index (no) at the center of each lens made with various glass compositions, the refractive index difference (Δn) between the center and the periphery, the numerical aperture (N, A,) and refractive index distribution of the lens are The ion exchange time required to achieve the ideal distribution (1
°E,) are shown in Tables 1 and 2.

第1表の「実施例」は本発明の組成範囲のガラスであり
、第2表の「比較例」はこれ以外のガラスである。画表
の対比から本発明に係る組成のガラスを使用した場合に
は、従来のガラスに比べて2倍以上大きい屈折率差を持
つレンズが得られるとともに、レンズの作製に要するイ
オン交換時間を1/3以下に短縮することができること
がわかる。(以下余白) 実施例2 モル%で、44.3  S t 02.14.3  C
520゜+2.5 82 03  、8.3  N82
01 1.6  K2 012.5   ZnO,6,
3PbO,0,05Sb203.0.15△3203か
らなる組成のガラスが得られるように実施例1と同様に
して原料を溶解、成型し、厚さ 3.0++unの板材
に加工後、硝酸カリウム溶融塩中に浸&i L/て屈伏
点付近(500℃)で176時間イオン交換を施し、し
かる後、適当な寸法に切り出し、両端面を研磨してスラ
ブレンズとした(第1図参照)。このスラブレンズは第
2図(A)、(B) 、(C)に示Mように、厚さ方向
の中心から外周部−Yo及びYOに向って一方向のみ徐
々に減少する屈折率分布を有しており、レンズ中心部(
P)の屈折率はn。−1,5624、当該部分と厚さ方
向周辺部分(Q)との屈折率差はΔn= 0.0302
9、間口数(N、Δ、) = 0.306のスラブレン
ズであった。
"Examples" in Table 1 are glasses having the composition range of the present invention, and "Comparative Examples" in Table 2 are glasses other than this. From the comparison of the graphs, when using the glass with the composition according to the present invention, a lens with a refractive index difference that is more than twice as large as that of conventional glass can be obtained, and the ion exchange time required to manufacture the lens can be reduced by 1. It can be seen that it can be shortened to /3 or less. (Left below) Example 2 In mol%, 44.3 S t 02.14.3 C
520°+2.5 82 03, 8.3 N82
01 1.6 K2 012.5 ZnO, 6,
The raw materials were melted and molded in the same manner as in Example 1 so as to obtain a glass having a composition of 3PbO, 0,05Sb203.0.15Δ3203. After processing into a plate with a thickness of 3.0++ un, it was poured into a potassium nitrate molten salt. The lens was immersed in water and subjected to ion exchange for 176 hours near the yield point (500°C), and then cut into appropriate dimensions and polished on both end faces to obtain a slab lens (see Figure 1). As shown in Figure 2 (A), (B), and (C), this slab lens has a refractive index distribution that gradually decreases in one direction from the center in the thickness direction toward the outer periphery -Yo and YO. The center of the lens (
The refractive index of P) is n. -1,5624, the refractive index difference between the relevant part and the peripheral part (Q) in the thickness direction is Δn = 0.0302
9. It was a slab lens with the number of frontages (N, Δ,) = 0.306.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は実施例2で得た幅2XO,厚さ2Yo、長さ2
Zoのスラブレンズの斜視図であり、第2図(A) 、
(B)及び(C)はそれぞれ第1図に示すスラブレンズ
のX方向、Y方向及びZ方向における屈折率分布を示す
。 出 願 人  ホーヤ株式会社
Figure 1 shows the width 2XO, thickness 2Yo, and length 2 obtained in Example 2.
FIG. 2(A) is a perspective view of Zo's slab lens;
(B) and (C) show the refractive index distribution in the X direction, Y direction, and Z direction of the slab lens shown in FIG. 1, respectively. Applicant Hoya Co., Ltd.

Claims (1)

【特許請求の範囲】 1 モル%で SiO_2 30〜75 Cs_2O 2〜25 ZnO 2〜40 Na_2O 0〜15 Li_2O 0〜15 K_2O 0〜15 B_2O_3 0〜15 Al_2O_3 0〜15 TiO_2 0〜15 ZrO_2 0〜7 Ta_2O_5 0〜5 Nb_2O_3 0〜7 WO_3 0〜5 La_2O_3+Y_2O_3 0〜15 CaO 0〜25 MgO 0〜25 SrO 0〜25 BaO 0〜25 PbO 0〜25 As_2O_3+Sb_2O_3 0〜0.5から成る
屈折率分布型透明体の製造に適したガラス組成物。
[Claims] In 1 mol%, SiO_2 30-75 Cs_2O 2-25 ZnO 2-40 Na_2O 0-15 Li_2O 0-15 K_2O 0-15 B_2O_3 0-15 Al_2O_3 0-15 TiO_2 0-15 ZrO_2 0-7 Ta_2O_5 0-5 Nb_2O_3 0-7 WO_3 0-5 La_2O_3+Y_2O_3 0-15 CaO 0-25 MgO 0-25 SrO 0-25 BaO 0-25 PbO 0-25 As_2O_3+Sb_2O_3 0-0.5 Gradient index transparent material A glass composition suitable for the production of.
JP14684985A 1985-07-05 1985-07-05 Glass composition suitable for producing transparent material of refractive index distribution type Pending JPS6212633A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14684985A JPS6212633A (en) 1985-07-05 1985-07-05 Glass composition suitable for producing transparent material of refractive index distribution type

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14684985A JPS6212633A (en) 1985-07-05 1985-07-05 Glass composition suitable for producing transparent material of refractive index distribution type

Publications (1)

Publication Number Publication Date
JPS6212633A true JPS6212633A (en) 1987-01-21

Family

ID=15416929

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14684985A Pending JPS6212633A (en) 1985-07-05 1985-07-05 Glass composition suitable for producing transparent material of refractive index distribution type

Country Status (1)

Country Link
JP (1) JPS6212633A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996027561A1 (en) * 1995-03-07 1996-09-12 Corning France S.A. High index glasses
JP2000159544A (en) * 1998-09-22 2000-06-13 Nippon Sheet Glass Co Ltd Glass composition, its production, substrate for information recording medium using the same, information recording medium and information recording apparatus
DE19920865C1 (en) * 1999-05-06 2000-06-29 Schott Glas Lead-free optical borosilicate glass, for optical equipment and optical data applications, contains barium, zinc, titanium, niobium and rare earth oxides and has a high refractive index and a low Abbe number
DE19958522A1 (en) * 1999-12-04 2001-06-21 Schott Glas Optical glasses containing zinc
EP1452495A2 (en) 2003-02-25 2004-09-01 Schott Glas Aluminosilicate glass
DE102007025601A1 (en) 2007-05-31 2008-12-04 Schott Ag Barium heavy-duty optical glasses
AU2010200124B2 (en) * 2009-02-13 2011-01-20 Schott Ag X-ray opaque barium-free glass and the use thereof
DE102010007796B3 (en) * 2010-02-12 2011-04-14 Schott Ag X-ray opaque barium-free glass and its use
KR101077686B1 (en) 2009-02-13 2011-10-27 쇼오트 아게 X-ray opaque barium-free glass and the use thereof
JP2012506607A (en) * 2008-10-24 2012-03-15 サン−ゴバン グラス フランス Glass substrate with electrodes, especially substrate used for organic light-emitting diode elements
US8268065B2 (en) 2009-02-13 2012-09-18 Schott Ag X-ray opaque barium-free glasses and uses thereof
CN104140204A (en) * 2013-05-09 2014-11-12 成都光明光电股份有限公司 Optical glass, optical preform and optical element

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5121594A (en) * 1974-08-16 1976-02-20 Sumitomo Shipbuild Machinery Suiso oyobi sansono seizoho

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5121594A (en) * 1974-08-16 1976-02-20 Sumitomo Shipbuild Machinery Suiso oyobi sansono seizoho

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996027561A1 (en) * 1995-03-07 1996-09-12 Corning France S.A. High index glasses
FR2731423A1 (en) * 1995-03-07 1996-09-13 Corning France GLASSES WITH HIGH REFRACTIVE INDEX
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