JPH02279537A - Ion exchange treatment of glass body - Google Patents
Ion exchange treatment of glass bodyInfo
- Publication number
- JPH02279537A JPH02279537A JP1097739A JP9773989A JPH02279537A JP H02279537 A JPH02279537 A JP H02279537A JP 1097739 A JP1097739 A JP 1097739A JP 9773989 A JP9773989 A JP 9773989A JP H02279537 A JPH02279537 A JP H02279537A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- ion exchange
- refractive index
- glass body
- monovalent cations
- 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
Links
- 239000011521 glass Substances 0.000 title claims abstract description 142
- 238000005342 ion exchange Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 36
- 150000001768 cations Chemical class 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011247 coating layer Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000010410 layer Substances 0.000 abstract description 23
- 230000003287 optical effect Effects 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 description 36
- 239000000203 mixture Substances 0.000 description 22
- 239000002002 slurry Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004927 clay Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- -1 sodium and potassium Chemical class 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 206010010071 Coma Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-LZFNBGRKSA-N Potassium-45 Chemical group [45K] ZLMJMSJWJFRBEC-LZFNBGRKSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910008649 Tl2O3 Inorganic materials 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QTQRFJQXXUPYDI-UHFFFAOYSA-N oxo(oxothallanyloxy)thallane Chemical group O=[Tl]O[Tl]=O QTQRFJQXXUPYDI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
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)
- Surface Treatment Of Glass (AREA)
- Optical Integrated Circuits (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、屈折率分布型レンズ等、一般にイオン濃度分
イＵを有するガラス体の中で、特に光軸方向屈折率分布
型レンズを製造する技術の改良に関する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention is particularly applicable to the production of gradient index lenses in the optical axis direction, among glass bodies that generally have an ion concentration of iU, such as gradient index lenses. related to improvements in technology.
一般に、外部からガラス体内部に特定のイオンを拡散さ
せて、このイオン分布によってガラス体の性質改変を行
う技術は広く用いられている０例えば、屈折率が相対的
に大なガラスの表面からガラスの屈折率減少に効果のあ
るナトリウムやカリウム等のイオンをガラスの内ｓｌｌ
に拡散させて、ガラス表面から内部に向かって屈折率が
次第に増加する屈折率分布をもつ屈折重分４ｆｆ型レン
ズを製造する方法、あるいは逆に屈折率が小なガラスか
ら成るガラスの表面から屈折率増加に効果のあるリチウ
ム、セシウム、銀、タリウム等のイオンをガラス内部に
拡散させて、ガラス表面から内部に向かって屈折率が次
第に減少する屈折率分布をもつ屈折率分布型レンズを製
造する方法がある。In general, the technique of diffusing specific ions from the outside into the inside of a glass body and modifying the properties of the glass body through this ion distribution is widely used. Ions such as sodium and potassium, which are effective in reducing the refractive index of glass, are added to the inside of the glass.
A method of manufacturing a refractive index 4FF type lens with a refractive index distribution in which the refractive index gradually increases from the glass surface toward the inside, or conversely, a method of manufacturing a refractive index 4FF type lens made of glass with a small refractive index. By diffusing ions such as lithium, cesium, silver, and thallium, which are effective in increasing the optical index, into the glass, a gradient index lens is manufactured that has a refractive index distribution in which the refractive index gradually decreases from the glass surface toward the inside. There is a way.
屈折率分布型レンズは大別して以下の３種に分類できる
。Gradient index lenses can be roughly classified into the following three types.
１）光軸方向屈折率分布型レンズ
２）半径方向屈折率分布型レンズ
３）球殻方向屈折率分布型レンズ
上記レンズの内、光軸方向屈折率分布型レンズを作製す
る方法は、まず屈折率が均一なガラス基板を作製し、こ
のガラス基板を溶融塩中に浸漬して１８１＆塩中の一価
陽イオンとガラス体中に含まれる一価陽イオンとを交換
させ、ガラス基板の表面から内部に向かって次第に減少
、または増加する屈折率分布を、そして、その表面に平
行な面内の屈折率は−様であるレンズ素材を作製する。1) Lens with gradient index in the optical axis direction 2) Lens with gradient index in the radial direction 3) Lens with gradient index in the spherical shell direction Among the above lenses, the method for producing the gradient index lens in the optical axis direction is to first use refraction. A glass substrate with a uniform ratio is prepared, and this glass substrate is immersed in molten salt to exchange the monovalent cations in the 181 salt with the monovalent cations contained in the glass body. A lens material is produced that has a refractive index distribution that gradually decreases or increases toward the inside, and that has a -like refractive index in a plane parallel to its surface.
このような屈折率分布を有するレンズ素材の両面を研Ｈ
し、所望の平面あるいは球面に加工することによって、
第４図に示すような光軸方向屈折率分布型レンズを作製
する事ができる。屈折率分布がガラス表面から内部に向
かってほぼ直線状に減少するレンズ素材から作製した平
凸レンズは、球面収差とコマ収差を良好に補正する作用
を有する。Polishing both sides of a lens material with such a refractive index distribution
By processing it into the desired flat or spherical surface,
A lens with a gradient index of refraction along the optical axis as shown in FIG. 4 can be manufactured. A plano-convex lens made from a lens material whose refractive index distribution decreases almost linearly from the glass surface toward the inside has the effect of effectively correcting spherical aberration and coma aberration.
上記平凸レンズの具体的な従来の作製方法は、ナトリウ
ムやカリウムを含む屈折率が均一なガラス基板を、屈折
率を高める作用の大きいタリウム等の一価陽イオンを含
む硝酸塩あるいは破酸塩等の溶融塩中に浸漬して、該溶
融塩中の一価陽イオンとガラス体中に含まれる一価陽イ
オンとを交換させ、ガラス基板表面から内部に向かって
屈折率が次第に減少する屈折率分布を形成させる。この
様にして得たレンズ素材を四角板状の小片に切断し、こ
れら小片を接着剤で相互に接着（貼り付け〉して四角柱
状体とする。この四角柱状体は円筒研削盤によって所望
の直径を有する円柱状体に加工（丸め）される。その後
、溶剤で接着剤を除去（バラク）すると円盤状レンズ素
材が多数得られる。The specific conventional manufacturing method for the above-mentioned plano-convex lens is to use a glass substrate with a uniform refractive index that contains sodium or potassium, and a nitrate or a salt containing monovalent cations such as thallium that have a large effect of increasing the refractive index. A refractive index distribution in which the refractive index gradually decreases from the surface of the glass substrate toward the inside by immersing it in a molten salt and exchanging monovalent cations in the molten salt with monovalent cations contained in the glass body. to form. The lens material obtained in this way is cut into square plate-like pieces, and these pieces are glued together (pasted) to form a square prism. It is processed (rounded) into a cylindrical body having a diameter.Then, the adhesive is removed (balked) with a solvent, and a large number of disc-shaped lens materials are obtained.
このレンズ素材のうち、屈折率分布を有する層を球面加
工し、屈折率分布が−様な面を平面に加工すると平凸の
光軸方向屈折率分布型レンズが得られる。Of this lens material, by processing the layer having a refractive index distribution into a spherical surface and processing the surface with a --like refractive index distribution into a flat surface, a plano-convex optical axis direction refractive index distribution type lens can be obtained.
前記ガラス基板から光軸方向屈折率分布型レンズを作製
する方法の最大の問題点は製造コストが高くつく事にあ
る。特に、丸め工程では四角柱状から円柱状に研削加工
するため貴重な硝材が少なくとも２２％は捨てられてし
まう事、また貼り付けやバラク工程等に多くの手間暇を
かけなければならない事にある。The biggest problem with the method of manufacturing a gradient index lens in the optical axis direction from the glass substrate is that the manufacturing cost is high. In particular, in the rounding process, at least 22% of valuable glass material is wasted as the glass is ground from a rectangular prism to a cylinder, and a lot of time and effort must be spent on pasting and barring processes.
一方、熱延伸法などで作製したガラス棒を切断して得た
円盤状ガラス板をイオン交換する方法は前述のガラス基
板から作製する方法に比べ、加工ロスが少ない様に考え
られるが、この方法では円！Ｉｉ１拭ガラス板の側周部
からのイオンの拡散があり、第３図に示すように半径方
向にも屈折率分布層を形成する。この屈折率分布層は光
軸方向屈折率分布型レンズにとって不要であるため、最
終的に研削除去しなければならず、前述の方法と同じく
貴重な硝材を浪費することになる。On the other hand, the method of ion-exchanging a disk-shaped glass plate obtained by cutting a glass rod produced by a hot drawing method etc. seems to have less processing loss than the method of producing it from a glass substrate as described above. So yen! There is diffusion of ions from the side periphery of the wipe glass plate Ii1, and a refractive index distribution layer is also formed in the radial direction as shown in FIG. Since this refractive index distribution layer is unnecessary for the optical axis direction refractive index distribution type lens, it must be finally removed by polishing, which wastes valuable glass material as in the above-mentioned method.
ガラス体と一価陽イオンを含む溶融塩とを接触させて、
溶融塩中のイオンとガラス体中に含まれる一価陽イオン
とを交換させるイオン交換処理方法において、イオン交
換処理に先立ち、被処理ガラス体の要部以外を、一価陽
イオンを、含まないガラスないしはガラス質の無機材か
ら成る被覆層で被覆する。By bringing the glass body into contact with a molten salt containing monovalent cations,
In an ion exchange treatment method in which ions in a molten salt are exchanged with monovalent cations contained in a glass body, prior to the ion exchange treatment, monovalent cations are not included in any part other than the main part of the glass body to be treated. Cover with a coating layer made of glass or a vitreous inorganic material.
１つの好適な方法は、二重ポット法、あるいはロッドイ
ンチューブ法によって芯体ガラスとこれを被覆する一価
陽イオンを含まない被覆ガラスとで円柱状のガラス棒を
形成し、このガラス棒を切断して側周面が上記被覆ガラ
ス層で被覆された円盤状ガラス板を作製してから該ガラ
ス板を溶融塩中に浸漬し、イオン交換処理を行う。One preferred method is to form a cylindrical glass rod with a core glass and a coating glass that does not contain monovalent cations by a double pot method or a rod-in-tube method, and then After cutting to produce a disc-shaped glass plate whose side peripheral surface is coated with the above-mentioned coating glass layer, the glass plate is immersed in molten salt and subjected to ion exchange treatment.
また他の好適な方法として、まず一価陽イオンを含まな
いガラスを溶解し、これを水中に投入して得た水砕カレ
ットを乾燥してからボールミルで粉砕してフリットを作
製する。このフリットに粘土及び水などを加えたスラリ
ーを被処理ガラスの表面に塗布し、ざらに乾燥と焼付け
を行なって被覆ガラス棒を形成する。次いで、この被覆
ガラス棒を切断して円盤状ガラス板を作製してからこれ
を溶融塩中に浸漬し、イオン交換処理を行なう。Another preferred method is to first melt glass that does not contain monovalent cations, and then pour it into water to obtain a granulated cullet, which is then dried and then ground in a ball mill to produce a frit. A slurry made by adding clay, water, etc. to this frit is applied to the surface of the glass to be treated, and is roughly dried and baked to form a coated glass rod. Next, this coated glass rod is cut to produce a disc-shaped glass plate, which is then immersed in molten salt to undergo ion exchange treatment.
この様な一価陽イオンを含まないガラスないしはガラス
質の無機材から成る被覆層（以下単に被覆ガラス層と呼
ぶ）が介在すると、該部位を介しての一価陽イオンの拡
散は極めて遅く、実質的に一価陽イオンの拡散は阻止さ
れる事が分かった。When a coating layer made of glass or a glassy inorganic material that does not contain monovalent cations (hereinafter simply referred to as a coating glass layer) is present, the diffusion of monovalent cations through the site is extremely slow; It was found that the diffusion of monovalent cations was substantially inhibited.
ただし、被覆ガラス層の厚みが厚すぎるとレンズの有効
径は小さくなり好ましくない、この観点から、前記被覆
ガラス層の厚みは約２５０μｍ以下のＲ囲が好ましい。However, if the thickness of the covering glass layer is too thick, the effective diameter of the lens becomes undesirably small.From this point of view, the thickness of the covering glass layer is preferably about 250 μm or less in radius radius.
上記の被覆ガラス層を有していない円盤状ガラス板では
、側周部からの一価陽イオンの拡散によって光軸方向以
外、即ち側周部付近では半径方向にも屈折率分布が形成
される。この屈折率分布は有害無益であるため後工程で
除去する必要が生じる。しかし、本発明の如く側周部が
一価陽イオンを含まない被覆ガラス層で覆われている円
盤状ガラス板では、イオン交換処理中に該ガラス板の側
周部からの一価陽イオンの透過がないため前記のような
半径方向の屈折率分布層は形成される事はなく、該側周
部を研削除去しなくても良い。In a disc-shaped glass plate without the above-mentioned coating glass layer, a refractive index distribution is formed in a direction other than the optical axis direction due to the diffusion of monovalent cations from the side periphery, that is, in the radial direction near the side periphery. . Since this refractive index distribution is harmful and useless, it is necessary to remove it in a subsequent process. However, in a disc-shaped glass plate whose side periphery is covered with a coating glass layer that does not contain monovalent cations as in the present invention, monovalent cations are removed from the side periphery of the glass plate during ion exchange treatment. Since there is no transmission, the radial refractive index distribution layer as described above is not formed, and there is no need to remove the side peripheral portion by polishing.
また、従来技術の様に四角板状の小片を接着剤で貼り合
わせて四角柱状体に作製したり、さらに円柱状体に研削
加工する必要も無くなるから貴重な硝材が有効に使える
ばかりでなく、かつ加工工程も少なくできる。そして、
前記被覆ガラス層が不必要な場合はレンズ加工時に芯取
りを行うことによって容易に除去することも出来る。In addition, there is no need to glue small pieces of square plates together with adhesive to create a square columnar body, or to grind them into a cylindrical body, as in the conventional technology, so not only can valuable glass materials be used more effectively, Moreover, the number of processing steps can be reduced. and,
If the covering glass layer is unnecessary, it can be easily removed by performing centering during lens processing.
以下本発明を図面に示した実施例に基づいて説明する。 The present invention will be described below based on embodiments shown in the drawings.
第１図は円盤状ガラス板Ｉを溶融塩３中に漫消し、イオ
ン交換を行っている様子を示している。ここで、被処理
ガラス体としてのガラス板ｌは、その側周部が一価陽イ
オンを透過しない被覆ガラス層２で被覆され、両者は完
全に熱融着して一体化した構造をしており、両面は露出
させである。溶融塩３に含まれる一価に２イオンＢ゛と
被処理ガラス体中の一価陽イオンＡ゛は、被処理ガラス
体１の表面のみを通してイオン交換が行われている。し
かし、その１Ｍｔ１部では一価陽イオンを透過しない被
覆ガラス層が存在するためこれらイオンの拡散は阻止さ
れる。この様な構造を有する円盤状ガラス板は、周知の
ロッドインチューブ法、あるいは二重水・シト法で作製
することができる。FIG. 1 shows a state in which a disk-shaped glass plate I is immersed in a molten salt 3 and ion exchange is performed. Here, the glass plate l as the glass body to be treated has a structure in which the side periphery thereof is covered with a coating glass layer 2 that does not transmit monovalent cations, and the two are completely thermally fused and integrated. Both sides are exposed. Ion exchange is performed between the monovalent diion B' contained in the molten salt 3 and the monovalent cation A' in the glass body 1 to be treated only through the surface of the glass body 1 to be treated. However, in the 1Mt portion, there is a covering glass layer that does not transmit monovalent cations, so the diffusion of these ions is blocked. A disc-shaped glass plate having such a structure can be produced by the well-known rod-in-tube method or the double water/sheet method.
あるいは、一価陽イオンを含まないガラスを粉砕して、
例えば３２５メツシユ以下のフリットを作製し、このフ
リットに粘土及び水などを加えたスラリーを被処理ガラ
ス棒の表面に塗布し、さらに乾燥と焼付けを行なったガ
ラス棒を切断する方法によっても作製できる。Alternatively, by crushing glass that does not contain monovalent cations,
For example, a frit of 325 mesh or less can be prepared, a slurry made by adding clay, water, etc. to the frit is applied to the surface of a glass rod to be treated, and the glass rod is further dried and baked and then cut.
次に、本発明の具体的な数値例について説明する。Next, specific numerical examples of the present invention will be explained.
実施例１ モル％（以下同じ）で表して、５ｉＯ２６０％。Example 1 Expressed as mol% (the same applies hereinafter), 5iO260%.
８２０３２％＋ ＺｎＯ１５％、ＺｒＯ２３％、Ｎａ
２ｏ ３％、ＫｔＯ１５％、ＴＩｒ０２％の組成を有
する直径が５０ｍｍ、長さが１ｍの母材ガラスを、 ５
ｉＯｚ６５％＋ ８２０３ ２５％、 ＺｎＯ１０
％の組成からなる内径が５５ｍｒｎ、外径が６８ｍｍの
被覆ガラス管に挿入し、その下端部を加熱して仮融着し
た。下端部は加熱したままで該ガラス管の上端を密刺し
、０．５気圧程度に減圧しなから熱延伸を行い、直径が
６．４ｍｍのガラスロッドを得た。該ロッドをスライシ
ングマシーンで３．２ｍｍの厚みに切断して円盤状ガラ
ス板を作製した。該ガラス板のイオン交換面の直径は６
゜Ｏｍｍで、側周部の被覆ガラス層の厚みは２００μｍ
であった。この円盤状ガラス板をＫＮＯ３９２％、Ｔｌ
ＮＯ３８％のｊＡ成からなる溶融塩中に浸漬して、４９
２℃で６９５時間イオン交換処理を行った。この様にし
て得られたレンズ素材の屈折率分布を調べたところ、第
２図に示す屈折率分布形状のしンズ素材が得られた。82032% + ZnO15%, ZrO23%, Na
A base glass with a diameter of 50 mm and a length of 1 m having a composition of 2O 3%, KtO 15%, and TIr 02%, 5
iOz65%+8203 25%, ZnO10
% composition and having an inner diameter of 55 mrn and an outer diameter of 68 mm, the lower end of the tube was heated and temporarily fused. The upper end of the glass tube was closely punctured while the lower end was still heated, and hot stretching was performed after reducing the pressure to about 0.5 atm to obtain a glass rod with a diameter of 6.4 mm. The rod was cut into a 3.2 mm thick piece using a slicing machine to produce a disc-shaped glass plate. The diameter of the ion exchange surface of the glass plate is 6
゜Omm, and the thickness of the coating glass layer on the side periphery is 200μm
Met. This disc-shaped glass plate was made of KNO392% and Tl.
49 by immersing it in a molten salt consisting of 38% NO and JA.
Ion exchange treatment was performed at 2°C for 695 hours. When the refractive index distribution of the lens material thus obtained was examined, a lens material having the refractive index distribution shape shown in FIG. 2 was obtained.
実施例２ Ｓｉ０２５７％ｌ Ｂ２Ｏ３３％、Ｍｇ０ ８％。Example 2 Si0257%l B2O33%, Mg08%.
Ｚｎ０１０％、 Ｎａ２Ｏ７％、 Ｋ２Ｏ１３％の組成
を有する母材ガラスと、５ｉ０２６０％、Ｂ２０３２０
％、Ｍｇ０ ５％、Ｚｎ０ １５％の組成からなる被覆
ガラスを、各々純白金製の二重ルツボの内ボットと外ポ
ットに入れて直径が３，８ｍｍのガラス棒を線引きした
。該ガラス棒をスライシングマシーンで１．８ｍｍの厚
みに切断して円盤状ガラス板を作製した。該ガラス板の
イオン交換面の直径は５．４ｍｍで、側周部の被覆ガラ
ス層の厚みは４９μｍであった。この円盤状ガラス板を
ＫＮＯ３９５％ル％、ＴｌＮＯ３５モル％の組成からな
る溶融塩中に浸漬して、４８５℃で７６０時間イオン交
換処理を行った。この様にして得られたレンズ素材の屈
折率分布を調べたところ、実施例】と同じ屈折率分布形
状を有するレンズ素材であった。Base material glass having a composition of Zn010%, Na2O7%, K2O13%, 5i0260%, B20320
%, Mg0 5%, and Zn0 15% were placed in the inner and outer pots of a double crucible made of pure platinum, respectively, and a glass rod with a diameter of 3.8 mm was drawn. The glass rod was cut into a 1.8 mm thick piece using a slicing machine to produce a disc-shaped glass plate. The diameter of the ion-exchange surface of the glass plate was 5.4 mm, and the thickness of the glass layer covering the side periphery was 49 μm. This disc-shaped glass plate was immersed in a molten salt having a composition of 395% KNO and 35 mol% TlNO, and was subjected to ion exchange treatment at 485° C. for 760 hours. When the refractive index distribution of the lens material thus obtained was examined, it was found that the lens material had the same refractive index distribution shape as in Example.
実施例３ Ｓｉ０２６０％、８２０３２％、ＺｎＯ１７％。Example 3 Si0260%, 82032%, ZnO17%.
ＺｒＯ２１％、Ｎａ２Ｏ３％、に２０ １７％の組成を
有する母材ガラスと、５ｉ０２３０％、８２０３３０％
、ＰｂＯ３０％、Ｂａ０ １０％の組成からなる被覆ガ
ラスを、実施例２と同様に二重ルツボ法で線引きし、外
径が４．３ｍｍのガラス棒を得た。該ガラス棒をスライ
シングマシーンで１゜８ｍｍの厚みに切断し′Ｃ円盤状
ガラス板を作製した。該ガラス板のイオン交換面の直径
は４．０ｍｍで、側周部の被覆ガラス層の厚みは１４６
μｍであった。この円盤状ガラス板をＫＮ ０３９７％
。Base material glass having a composition of 21% ZrO, 3% Na2O, 20% to 17%, 5i0230%, 820330%
, 30% PbO, and 10% Ba0 was drawn using the double crucible method in the same manner as in Example 2 to obtain a glass rod with an outer diameter of 4.3 mm. The glass rod was cut into 1.8 mm thick pieces using a slicing machine to produce 'C' disk-shaped glass plates. The diameter of the ion exchange surface of the glass plate is 4.0 mm, and the thickness of the coating glass layer on the side periphery is 146 mm.
It was μm. This disc-shaped glass plate is made of KN 0397%
.
ＴｌＮＯ３３％の組成からなる溶融塩中に浸漬して、４
８５℃で７６０時間イオン交換処理を行った。この様に
して得、られたレンズ素材の屈折率分布を調べたところ
、実施例１と同じ屈折率分布形状を有するレンズ素材で
あった。4 by immersing it in a molten salt having a composition of 3% TlNO.
Ion exchange treatment was performed at 85°C for 760 hours. When the refractive index distribution of the lens material thus obtained was examined, it was found that the lens material had the same refractive index distribution shape as Example 1.
実施例４ Ｓｉ０２６０％＋ ８２０３５％、Ｍｇ０ ２％。Example 4 Si0260% + 82035%, Mg02%.
ＺｎＯ１１％、Ｎａ２Ｏ５％、に２０ １２％、Ｔｌ２
Ｏ３％の組成を有する心材ガラスと、５ｉ０２２０％＋
８２０３３０％、ＰｂＯ４０％、 Ｚｎ０ １０
％の組成からなる被覆ガラスを、実施例２と同じく二重
ルツボ法で線引きし、外径が４゜０ｍｍのガラス棒を得
た。該ガラス棒をスライシングマシーンで１．８ｍｍの
厚みに切断して円盤状ガラス板を作製した。該側周部の
被覆ガラス層の厚みは１５μｍであった。この円盤状ガ
ラス板をＫＮＯ３９５％、ＴｌＮＯ３５％の組成からな
る溶融塩中に浸漬して、４８５℃で７６０時間イオン交
換処理を行った。この様にして得られたレンズ素材の屈
折率分布を調べたところ、実施例１と同じ屈折率分布形
状のレンズ素材である事が確認された。ZnO 11%, Na2O 5%, Ni20 12%, Tl2
Core glass having a composition of O3% and 5i0220%+
820330%, PbO40%, Zn0 10
% was drawn using the double crucible method as in Example 2 to obtain a glass rod with an outer diameter of 4.0 mm. The glass rod was cut into a 1.8 mm thick piece using a slicing machine to produce a disc-shaped glass plate. The thickness of the glass layer covering the side circumference was 15 μm. This disc-shaped glass plate was immersed in a molten salt having a composition of 395% KNO and 35% TlNO, and was subjected to ion exchange treatment at 485° C. for 760 hours. When the refractive index distribution of the lens material thus obtained was examined, it was confirmed that the lens material had the same refractive index distribution shape as Example 1.
実施例５ モル％で表して、５ｉＯ２６０％、ＢｚＯｔ２％。Example 5 Expressed in mol%, 5iO2 60%, BzOt2%.
ＺｎＯ１５％、ＺｒＯ２２％＋ ＮａａＯ３％、に２
０１５％、Ｔｌ２０２％の組成を（Ｔする直径が１、ｆ
）ｍｍ、単長１ｍの被処理ガラス棒を、モル％で表して
、５ｉ０２３０％、８２０３ ２８％、Ｐｂ０４０％、
ＺｒＯ２２％の組成を有するフリット１００重量部に対
し、粘土６重量部、カルボキシメチルセルローズ２蚤型
部と水４５重量部を加え十分混合して得たスラリーの中
に浸漬して、被処理ガラス棒の表面にスラリーを塗布し
た。該ガラス棒を１２０℃で乾燥後、４９５℃迄昇温し
、２時間ｖＥ成した。冷却後、該ガラス棒をスライシン
グマシーンで２．２ｍｍの厚みに切断して円盤状ガラス
板を作製した。その側周部の被覆ガラス層の厚みは９５
μｍであった。この円盤状ガラス板をモル％で表して、
ＫＮＯ３９２％、ＴｌＮ０１８％の組成からなる溶融塩
中に浸漬して、４９２℃で６９５時間イオン交換処理を
行った。この様にして得られたレンズ素材の屈折率分布
を調べたところ、第２図に示す屈折率分布形状を有する
レンズ素材が得られた。ZnO15%, ZrO22% + NaaO3%, 2
015%, Tl202% composition (T diameter is 1, f
) mm, the glass rod to be treated with a single length of 1 m is expressed in mol%, 5i0230%, 8203 28%, Pb040%,
To 100 parts by weight of frit having a composition of 22% ZrO, 6 parts by weight of clay, 2 parts by weight of carboxymethyl cellulose and 45 parts by weight of water were added and thoroughly mixed.The glass rod to be treated was immersed in the slurry obtained. The slurry was applied to the surface. After drying the glass rod at 120°C, the temperature was raised to 495°C and vE was performed for 2 hours. After cooling, the glass rod was cut into a 2.2 mm thick piece using a slicing machine to produce a disk-shaped glass plate. The thickness of the coating glass layer around the side is 95
It was μm. This disc-shaped glass plate is expressed in mol%,
It was immersed in a molten salt having a composition of 392% KNO and 18% TlN, and was subjected to ion exchange treatment at 492°C for 695 hours. When the refractive index distribution of the lens material thus obtained was examined, a lens material having the refractive index distribution shape shown in FIG. 2 was obtained.
実施例６
モル％で表して、５ｉＯ２６７％＋ Ｂ２０ｉ ５％
。Example 6 5iO2 67% + B20i 5% expressed in mol%
.
Ｍｇ０ ８％、ＺｎＯ１０％、Ｎａ２Ｏ７％、に２０１
３％の組成を有する直径が３． ８ｍｍ、単長１ｍの被
処理ガラス棒を、モル％で表して、５ｉ０２３５％！
８２０３３０％、Ｐｂ０ ３０％。Mg0 8%, ZnO 10%, Na2O 7%, 201
3. diameter with a composition of 3%. The glass rod to be treated with a diameter of 8 mm and a length of 1 m is expressed as mol%, and is 5i0235%!
820330%, Pb0 30%.
Ａ１２０３５％の組成を有するフリッ）１００２１１１
：部に対し、粘土５重量部、カルボキシメチルセルロー
ズ１重ｔｇｌ＋、塩化カリウム０．５ｆｉｍ部と水４５
盃量部を加え十盆混合して得たスラリーの中に浸漬して
、被処理ガラス棒の表面にスラリーを２度塗布した。該
ガラス棒を１２０℃で乾燥後、４９５℃迄昇温し、２時
間焼成した。冷却後、該ガラス棒をスライシングマシー
ンで１．８ｍｍの厚みに切断して円盤状ガラス板を作製
した。その側周部の被覆ガラス層の厚みは１Ｂ５μｒｎ
であった。この円盤状ガラス板をモル％で表して、ＫＮ
Ｏ３９５％、ＴｌＮ０ａ５％の組成からなる溶融塩中に
浸漬して、４８５℃で６９５時間イオン交換処理を行っ
た。この様にして得られたレンズ素材の屈折率分布を調
べたところ、実施例１と同じ屈折率外イ１形状のレンズ
素材である事が確認された。A1002111 with a composition of 35%
: 5 parts by weight of clay, 1 weight part of carboxymethyl cellulose TGL+, 0.5 fim part of potassium chloride, and 45 parts of water.
The glass rod to be treated was immersed in the slurry obtained by adding a glass rod and mixing in ten trays, and the slurry was applied twice to the surface of the glass rod to be treated. After drying the glass rod at 120°C, the temperature was raised to 495°C and fired for 2 hours. After cooling, the glass rod was cut into a 1.8 mm thick piece using a slicing machine to produce a disk-shaped glass plate. The thickness of the coating glass layer around the side is 1B5μrn
Met. Expressing this disc-shaped glass plate in mol%, KN
It was immersed in a molten salt having a composition of 95% O3 and 5% TlN0a, and was subjected to ion exchange treatment at 485°C for 695 hours. When the refractive index distribution of the lens material thus obtained was examined, it was confirmed that the lens material had the same refractive index outside A1 shape as in Example 1.
実施例７ モル％で表して、５ｉｎ２５Ｑ％、８２０３２％。Example 7 Expressed in mol%, 5in25Q%, 82032%.
ＺｎＯ１７％、ＺｒＯ２１％、Ｎａ２Ｏ３％、に２０１
７％の組成を有する直径が５． ０ｍｍ、単長１ｍの被
処理ガラス棒を、モル％で表して、５ｉ０２１７％、１
３２０３２５％、ＰｂＯ５０％。ZnO17%, ZrO21%, Na2O3%, 201
5. diameter with a composition of 7%. A glass rod to be treated with a diameter of 0 mm and a length of 1 m is expressed as mol%, 5i0217%, 1
320325%, PbO50%.
Ａｌ２０ａ８％の組成を有するフリット１００重量部に
刻し、粘土７重ＰＩｋ部と水４７重量部を加え十分混合
して得たスラリー〇中に浸漬して、被処理ガラス棒の表
面にスラリーを塗布した。該ガラス棒な１２０℃で乾燥
後、４９５℃迄昇温し、２時間焼成した。冷却後、該ガ
ラス棒をスライシングマシーンで１．８ｍｍの厚みに切
断して円盤状ガラス板を作製した。その側周部の被覆ガ
ラス層の厚みは３５μｍであった。この円盤状ガラス板
をモル％で表して、ＫＮＯ３９７％、ＴｌＮＯ３３％の
組成からなる溶融塩中に浸漬して、４９２℃で４９０時
間イオン交換処理を行った。この様にして得られたレン
ズ素材の屈折率分布を調べたところ、実施例１と同じ屈
折率分布形状のレンズ素材であった。Cut into 100 parts by weight frit having a composition of 8% Al20a, add 7 parts PIk of clay and 47 parts by weight of water, and thoroughly mix it. Dip it into the slurry 〇 obtained, and apply the slurry to the surface of the glass rod to be treated. did. After drying the glass rod at 120°C, the temperature was raised to 495°C and fired for 2 hours. After cooling, the glass rod was cut into a 1.8 mm thick piece using a slicing machine to produce a disk-shaped glass plate. The thickness of the covering glass layer at the side circumference was 35 μm. This disc-shaped glass plate was immersed in a molten salt having a composition of 397% KNO and 33% TlNO expressed in mol%, and was subjected to ion exchange treatment at 492° C. for 490 hours. When the refractive index distribution of the lens material thus obtained was examined, it was found that the lens material had the same refractive index distribution shape as in Example 1.
実施例８
モル％て表して、５ｉＯａ６２％、８２０３５％Ｍｇ０
２％、ＺｎＯ１１％、Ｎａ２Ｏ５％、に２０１２％、
Ｔｌ２Ｏ３％の組成を有する直径が３．５ｍｍ、単長１
ｍの被処理ガラス棒を、モル％で表して、５ｔ０２２０
％、ＢＰＯ４２０％、Ｐｂｏ ５５％、Ａ Ｉ ２０
３５％の組成を有するフリツ）１００ｆｆｉｆｆｉ部に
対し、粘土１０ｉｆｔｆｆｔ部と水５０重量部を加え十
分混合して得たスラリーの中に浸漬して、被処理ガラス
棒の表面にスラリーを塗布した。該ガラス棒を１２０℃
で乾燥後、４９５℃迄昇温し、２時間焼成した。冷却後
、該ガラス棒をスライシングマシーンで１．８ｍｍの厚
みに切断して円盤状ガラス板を作製した。その側周部の
被覆ガラス層の厚みは３３μｍであった。この円盤状ガ
ラス板をモル％で表して、ＫＮＯ３９７％、ＴｌＮ０ｒ
３％の組成からなる溶融塩中に浸漬して、４９２℃で６
９５時間イオン交換処理を行った。この様にして得られ
たレンズ素材の屈折率分布を調べたところ、実施例１と
同じ屈折率分布形状のレンズ素材が得られた。Example 8 Expressed as mol%, 5iOa62%, 82035%Mg0
2%, ZnO11%, Na2O5%, 2012%,
A diameter of 3.5 mm and a single length of 1 with a composition of Tl2O3%
m of glass rods to be treated, expressed as mol%, 5t0220
%, BPO420%, Pbo 55%, AI 20
The glass rod to be treated was immersed in a slurry obtained by adding 10 iffft parts of clay and 50 parts by weight of water to 100 ffiffi parts having a composition of 35%, and applying the slurry to the surface of the glass rod to be treated. The glass rod was heated to 120℃
After drying, the temperature was raised to 495°C and baked for 2 hours. After cooling, the glass rod was cut into a 1.8 mm thick piece using a slicing machine to produce a disk-shaped glass plate. The thickness of the covering glass layer at the side circumference was 33 μm. Expressing this disk-shaped glass plate in mol%, KNO397%, TlN0r
It was immersed in a molten salt with a composition of 3% and heated at 492°C for 6 hours.
Ion exchange treatment was performed for 95 hours. When the refractive index distribution of the lens material thus obtained was examined, a lens material with the same refractive index distribution shape as in Example 1 was obtained.
比較例１
実施例１と同じ母材ガラスのみを熱延伸して得たガラス
ロッドをスライシングマシーンで切断して、直径が６．
０ｍｍ、厚みが３．２ｍｍの円盤状ガラス板を作製し
て、実施例１と同じ？ｄｌｉｉ！塩中で、かつ同じ条件
でイオン交換したレンズ素材の屈折率分布を調べたとこ
ろ、前記ガラス板の側周部からの一価陽イオンの拡散が
あるため、第３図に示す擾に側周部で半径方向の屈折率
分布が形成されている事が確認された。Comparative Example 1 A glass rod obtained by hot-stretching only the same base material glass as in Example 1 was cut with a slicing machine to a diameter of 6.5 mm.
A disk-shaped glass plate with a thickness of 3.2 mm and a thickness of 3.2 mm was prepared in the same manner as in Example 1. dliii! When we investigated the refractive index distribution of a lens material subjected to ion exchange in salt under the same conditions, we found that monovalent cations diffused from the side periphery of the glass plate. It was confirmed that a radial refractive index distribution was formed in the area.
比較例２
実施例１と同じ組成の直径が４− Ｏｍｒｎ、 単
長が１ｍの被処理ガラス棒をスライシングマシーンで切
断して、厚みが２．２ｍｍの円盤状ガラス板を作製して
、実施例１と同じ）７Ｊ融塩中で、かつ同じ条件でイオ
ン交換したレンズ素材の屈ｔＲｉ１分布を調べたところ
、前記カラス板の側周部からの一価陽イオンの拡散が起
こり、第３図に示す様に側周部で半径方向の屈折率分布
が形成されている事が確認された。Comparative Example 2 A glass rod to be treated having the same composition as Example 1 and having a diameter of 4-Omrn and a unit length of 1 m was cut with a slicing machine to produce a disc-shaped glass plate with a thickness of 2.2 mm. When we investigated the flexural tRi1 distribution of the lens material subjected to ion exchange in 7J molten salt under the same conditions as in 1), we found that monovalent cations diffused from the side periphery of the glass plate, as shown in Figure 3. As shown, it was confirmed that a radial refractive index distribution was formed at the side periphery.
本発明によれば、硝材を浪費することがなく、効率良く
レンズ素材を作製することができる。また、製造工程を
少なくすることも可能になるため光軸方向屈折率分布型
レンズが効率良く、かつ安価に製造できる。According to the present invention, lens materials can be efficiently produced without wasting glass materials. Further, since it is possible to reduce the number of manufacturing steps, the optical axis direction gradient index lens can be manufactured efficiently and at low cost.
第１図は本発明によって作製した円盤状ガラス板のイオ
ン交換処理工程を示す断面図、第２図（ａ）は本発明に
よるイオン交換処理後の円盤状ガラス板の断面図、同図
（ｂ）はその側周部（破線Ｉｇ）の屈折率分布形状を示
す図、第３図（ａ）は従来法によるイオン交換処理後の
円盤状ガラス板の断面図、同図（ｂ）はその側周部（破
線部）の屈折率分布形状を示す図、第４図は平凸の光軸
方向屈折率分布型レンズを示す断面図である。
１・・・・・被処理ガラス体 ２・・・・・被覆ガ
ラス層３・・・・・溶融塩FIG. 1 is a cross-sectional view showing the ion exchange treatment process of a disc-shaped glass plate produced according to the present invention, FIG. ) is a diagram showing the refractive index distribution shape of the side circumference (broken line Ig), Figure 3 (a) is a cross-sectional view of the disc-shaped glass plate after ion exchange treatment by the conventional method, and Figure 3 (b) is the side thereof. FIG. 4 is a cross-sectional view showing a plano-convex optical axis direction gradient index lens. 1... Glass body to be treated 2... Covering glass layer 3... Molten salt
Claims (1)
該イオンとガラス体中に含まれる一価陽イオンとを交換
させるイオン交換処理方法において、イオン交換処理に
先立ち、前記ガラス体の要部以外を、一価陽イオンを含
まないガラスないしはガラス質無機材から成る被覆層で
被覆することを特徴とするガラス体のイオン交換処理方
法。By bringing the glass body into contact with a molten salt containing monovalent cations,
In an ion exchange treatment method in which the ions are exchanged with monovalent cations contained in the glass body, prior to the ion exchange treatment, other than the main parts of the glass body are treated with glass that does not contain monovalent cations or vitreous material. A method for ion exchange treatment of a glass body, characterized by coating it with a coating layer made of a material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1097739A JPH02279537A (en) | 1989-04-18 | 1989-04-18 | Ion exchange treatment of glass body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1097739A JPH02279537A (en) | 1989-04-18 | 1989-04-18 | Ion exchange treatment of glass body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02279537A true JPH02279537A (en) | 1990-11-15 |
Family
ID=14200266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1097739A Pending JPH02279537A (en) | 1989-04-18 | 1989-04-18 | Ion exchange treatment of glass body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02279537A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1989
- 1989-04-18 JP JP1097739A patent/JPH02279537A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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