JP5099890B2 - Optical glass - Google Patents
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- JP5099890B2 JP5099890B2 JP2007178432A JP2007178432A JP5099890B2 JP 5099890 B2 JP5099890 B2 JP 5099890B2 JP 2007178432 A JP2007178432 A JP 2007178432A JP 2007178432 A JP2007178432 A JP 2007178432A JP 5099890 B2 JP5099890 B2 JP 5099890B2
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本発明は光学ガラスに関し，特に高屈折率及び低屈伏点で且つ，成形時の耐失透性が改善された，モールド成形及び微細構造の転写に適した組成を有する光学ガラスに関する。 The present invention relates to an optical glass, and more particularly to an optical glass having a composition suitable for molding and fine structure transfer, which has a high refractive index, a low yield point and improved devitrification resistance during molding.
近年，光学機器の小型軽量化が著しく進展している中で，非球面レンズが多く用いられるようになってきている。これは，非球面レンズは光線収差の補正が容易であり，レンズの枚数を少なくし，機器をコンパクトにすることができるためである。さらに非球面レンズ以外への用途も開発されてきており，金型の微細構造を精度良く転写できることが望まれている。 In recent years, aspherical lenses are increasingly used as optical devices are becoming smaller and lighter. This is because the aspherical lens can easily correct the light aberration, reduce the number of lenses, and make the device compact. Furthermore, applications other than aspherical lenses have been developed, and it is desired that the microstructure of the mold can be accurately transferred.
非球面レンズの製造は，ガラスのプリフォームを加熱軟化させ，これを所望形状に精密モールドプレス成形することによってなされている。プリフォームを得る方法は大きく２種類に分けられ，一つはガラスのブロックあるいは棒材等からガラス片を切り出してプリフォーム加工する方法，もう一つはガラス融液をノズル先端から滴下して球状のガラスプリフォームを得る方法である。 Aspherical lenses are manufactured by heating and softening a glass preform and precision molding press molding it into a desired shape. There are two main methods for obtaining preforms: one is to cut glass pieces from glass blocks or rods, and the other is preform processing. The other is to drop glass melt from the tip of a nozzle to make a spherical shape. This is a method for obtaining a glass preform.
精密モールドプレス成形によってガラス成形品を得るためには，プリフォームの加圧成形を屈伏点（Ａｔ）近傍の温度で行うことが必要である。このため，プリフォームの屈伏点（Ａｔ）が高いほど，これに接する金型が一層の高温に曝されることとなり，金型表面が酸化消耗し，金型のメンテナンスが必要となり，低コストでの大量生産が実現できなくなる。このため，プリフォームを構成する光学ガラスは，比較的低温で成形できること，従って，ガラス転移点（Ｔｇ）及び／又は屈伏点（Ａｔ）が低いことが望まれている。 In order to obtain a glass molded product by precision mold press molding, it is necessary to perform pressure molding of the preform at a temperature in the vicinity of the yield point (At). For this reason, the higher the yield point (At) of the preform, the more the mold in contact with it will be exposed to higher temperatures, the mold surface will be oxidized and consumed, and maintenance of the mold will be required. Mass production cannot be realized. For this reason, it is desired that the optical glass constituting the preform can be molded at a relatively low temperature, and therefore has a low glass transition point (Tg) and / or yield point (At).
一方，モールドレンズに用いられるガラスとしては，その用途に応じて種々の光学特性を有するものが求められており，中でも高屈折率でかつ低屈伏点の光学特性を有するものの要求が高まっている。そのような光学特性を満たすガラスとしてＳＦタイプのガラスがあるが，人体に有害なＰｂＯを含有するばかりでなく，精密プレス成形時に金属鉛が製品の表面に析出するため好ましくない。 On the other hand, as glass used for a mold lens, a glass having various optical characteristics is required depending on its use. In particular, there is an increasing demand for a glass having a high refractive index and a low yield point. An SF type glass is available as a glass that satisfies such optical characteristics. However, it is not preferable because it contains not only PbO harmful to the human body but also metal lead precipitates on the surface of the product during precision press molding.
ＰｂＯを含有しない上記の光学特性を有するガラスとしてＰ2Ｏ5−Ｂ2Ｏ3−ＧｅＯ2−Ｎｂ2Ｏ5−Ｂｉ2Ｏ3−Ｒ2Ｏ系ガラス（Ｒ＝Ｎａ，Ｋ，Ｌｉ）で，１．８３以上という屈折率を持った精密プレス用光学ガラスが報告されている（特許文献１参照）。しかしながら，このガラスには，精密モールドプレス成形したとき成形品の成形表面が白濁し易いという問題がある。また，Ｐ2Ｏ5−Ｂ2Ｏ3−ＴｉＯ2−Ｎｂ2Ｏ5−ＷＯ3−Ｒ2Ｏ系ガラス（Ｒ＝Ｎａ，Ｋ，Ｌｉ）も酸化鉛を含有しない上記の光学特性を有するガラスとして知られているが（特許文献２参照），このガラスは，紫色に着色しやすい上に，精密モールドプレス成形したときやはり成形表面が白濁し易いという問題がある。特に，これらのガラスの成形で発生する成形表面の白濁は，成形品の透明性を失わせ不良品を与えるため，これらのガラスを精密モールドプレス成形によるモールドレンズの大量生産に用いることは，不可能である。そのような白濁の発生は，主として成形時の加圧によって表面失透が発生することによるものであることが確認されており，その発生の度合いはプリフォームの作製方法や金型表面の状態によっても大きく左右される。 P 2 O as a glass having the above optical properties that do not contain PbO 5 -B 2 O 3 -GeO 2 -Nb 2 O 5 -Bi 2 O 3 -R 2 O -based glass (R = Na, K, Li ) in An optical glass for precision presses having a refractive index of 1.83 or more has been reported (see Patent Document 1). However, this glass has a problem that the molding surface of the molded product tends to become cloudy when precision mold press molding is performed. Further, P 2 O 5 —B 2 O 3 —TiO 2 —Nb 2 O 5 —WO 3 —R 2 O-based glass (R = Na, K, Li) is a glass having the above optical characteristics that does not contain lead oxide. (Refer to Patent Document 2), however, this glass has a problem that it tends to be colored purple, and the molding surface tends to become cloudy when precision mold press molding is performed. In particular, the cloudiness of the molding surface that occurs during the molding of these glasses loses the transparency of the molded product and gives a defective product. Therefore, it is not possible to use these glasses for mass production of mold lenses by precision mold press molding. Is possible. It has been confirmed that such cloudiness is mainly due to surface devitrification caused by pressure during molding, and the degree of occurrence depends on the preform preparation method and the mold surface condition. Is also greatly affected.
更に，アルカリ金属酸化物とＰ2Ｏ5，Ｂ2Ｏ3，Ａｌ2Ｏ3等を含みＰｂＯを含まないプレス成形レンズ用光学ガラスが報告されているものの（特許文献３参照），このガラスは，Ｂｉ2Ｏ3を比較的多く使用しており，精密モールドプレス後にＢｉ2Ｏ3の還元による着色とＢｉ2Ｏ3が原因と思われるガラス表面の荒れが生じやすいため，近年期待されている高屈折率，低屈伏点のモールドガラスの条件を十分には満たしていない。
上記のように，ＰｂＯの代替成分としてＢｉ2Ｏ3を含有するガラスは精密モールドプレス成形したとき成形表面に荒れが生じやすいという問題がある，という背景において，本発明は，高屈折率（特に好ましくは屈折率１．６５以上）という光学特性を有すると共に，低屈伏点であり，人体に有害なＰｂＯを含まず，しかも成形表面の白濁や荒れの発生が防止される，精密モールドプレス成形に適した光学ガラスを提供することを目的とする。 As described above, in the background that glass containing Bi 2 O 3 as an alternative component of PbO is prone to roughening on the molding surface when precision mold press molding is performed, the present invention has a high refractive index (particularly, For precision mold press molding, which has optical properties (preferably a refractive index of 1.65 or more), a low yield point, does not contain PbO harmful to the human body, and prevents generation of white turbidity and roughness on the molding surface. An object is to provide a suitable optical glass.
上記課題を解決するため，本発明者は研究を重ねた結果，ガラスの製造にあたってその組成を特定範囲のものとすること，具体的にはガラス成分のＺｎＯとＧｅＯ2を増量させることによって，Ｂｉ2Ｏ3に伴う成形品の成形表面の荒れの発生を抑制することができると共に，上記の光学特性を有し，ガラス転移温度（Ｔｇ）及びガラス屈伏点（Ａｔ）が低く，かつ精密モールドプレス成形で成形表面に白濁等の欠陥が生じにくいという特徴を有する，低コストの精密プレス成形レンズ用ガラスが得られることを見出し，本発明を完成させた。 In order to solve the above-mentioned problems, the present inventor has made researches. As a result, the composition of the glass is made within a specific range in manufacturing the glass, specifically, by increasing the amounts of the glass components ZnO and GeO 2. 2 O 3 can suppress the occurrence of surface roughness of the molded product, has the above optical characteristics, low glass transition temperature (Tg) and glass yield point (At), and precision mold press The present inventors have found that a low-cost glass for precision press-molded lenses having the feature that defects such as cloudiness hardly occur on the molding surface by molding can be obtained.
すなわち，本発明は，以下を提供するものである。
１．ガラス組成として，重量％で
Ｐ2Ｏ5：１８〜３２％
Ｂ2Ｏ3：０〜８％
ＧｅＯ2：５〜２０％
Ａｌ2Ｏ3：０．１〜１０％
ＺｎＯ：８〜３０％
ＴｉＯ2：０〜３％
Ｎｂ2Ｏ5：４〜３０％
ＷＯ3：１〜１２％
Ｂｉ2Ｏ3：３〜４５％
Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ：６〜１８％
（但し，Ｌｉ2Ｏ：０．１〜８％，Ｎａ2Ｏ：２〜１８％，Ｋ2Ｏ：０〜１０％）
ＢａＯ：１．３〜１５％
ＭｇＯ＋ＣａＯ＋ＳｒＯ：０．５〜１０％
（但し，ＭｇＯ：０．１〜５％，ＣａＯ：０〜５％，ＳｒＯ：０．５〜５％）
ＮａＦ：０〜１０％
ＺｎＦ：０〜１０％
を含んでなることを特徴とする光学ガラス。
２．ガラス組成として，重量％で
Ｇｄ2Ｏ3：０〜３％
Ｙｂ2Ｏ3：０〜３％
ＺｒＯ2 ：０〜３％
Ｔａ2Ｏ5：０〜３％
（但し，Ｇｄ2Ｏ3＋Ｙｂ2Ｏ3＋ＺｒＯ2＋Ｔａ2Ｏ5：０．１〜３％）
を更に含んでなることを特徴とする，上記１の光学ガラス。
３．ガラス組成として，重量％でＴｅＯ2を１０％以下の量で含んでなることを特徴とする，上記１又は２の光学ガラス。
４．屈折率（ｎd）が１．６５〜１．８０，ガラス転移点（Ｔｇ）が４００〜４９０℃，ガラス屈伏点（Ａｔ）が４４０〜５５０℃である，上記１ないし３の何れかの光学ガラス。
That is, the present invention provides the following.
1. As a glass composition, P 2 O 5 : 18 to 32% by weight
B 2 O 3: 0~8%
GeO 2 : 5 to 20%
Al 2 O 3 : 0.1 to 10%
ZnO: 8-30%
TiO 2: 0~3%
Nb 2 O 5 : 4-30%
WO 3: 1~12%
Bi 2 O 3 : 3 to 45%
Li 2 O + Na 2 O + K 2 O: 6 to 18%
(However, Li 2 O: 0.1~8%, Na 2 O: 2~18%, K 2 O: 0~10%)
BaO: 1.3-15%
MgO + CaO + SrO: 0.5-10%
(However, MgO: 0.1-5%, CaO: 0-5%, SrO: 0.5-5%)
NaF: 0 to 10%
ZnF: 0 to 10%
An optical glass comprising:
2. As a glass composition, Gd 2 O 3 by weight%: 0 to 3%
Yb 2 O 3 : 0 to 3%
ZrO 2 : 0 to 3%
Ta 2 O 5 : 0 to 3%
(However, Gd 2 O 3 + Yb 2 O 3 + ZrO 2 + Ta 2 O 5 : 0.1 to 3%)
The optical glass of 1 above, further comprising:
3. The optical glass according to 1 or 2 above, wherein the glass composition contains TeO 2 in an amount of 10% or less by weight.
4). The optical system according to any one of 1 to 3 above, wherein the refractive index (n d ) is 1.65 to 1.80, the glass transition point (Tg) is 400 to 490 ° C., and the glass yield point (At) is 440 to 550 ° C. Glass.
上記各組成になる本発明によれば，屈折率（ｎd）が１．６５〜１．８０，人体に有毒なＰｂＯを含まず，しかも精密モールドプレス時に成形表面で白濁が生じにくい，従って精密モールドプレス成形品の大量生産に適した光学ガラスを得ることができる。 According to the present invention comprising the above composition, refractive index (n d) from 1.65 to 1.80, free of toxic PbO to the human body, yet opaque and molding surface is less likely to occur during precision press molding, thus precisely Optical glass suitable for mass production of molded press-molded products can be obtained.
本発明において，屈折率（ｎｄ）とは，ヘリウムの５８７．６ ｎｍの輝線に対する屈折率をいう。本発明のガラスにおいて，屈折率は好ましくは１．６５〜１．８０の範囲にあり，より好ましくは１．６８〜１．７８の範囲にある。 In the present invention, the refractive index (nd) means the refractive index of helium with respect to the 587.6 nm emission line. In the glass of the present invention, the refractive index is preferably in the range of 1.65 to 1.80, more preferably in the range of 1.68 to 1.78.
また，本発明において，アッベ数（νd）は，νd＝（ｎd−１）／（ｎF−ｎc）で定義され，ｎF，ｎCはそれぞれ水素の４８６．１ｎｍ及び６５６．３ｎｍの輝線に対する屈折率である。 In the present invention, the Abbe number (ν d ) is defined by ν d = (n d −1) / (n F −n c ), and n F and n C are 486.1 nm and 656. Refractive index for 3 nm emission line.
また，屈伏点（Ａｔ）とは，熱機械分析装置（ＴＭＡ）で熱膨張測定をしたとき，ガラスの軟化によって，膨張曲線が上昇から下降に転じる極大点である。 The yield point (At) is the maximum point at which the expansion curve changes from rising to falling due to softening of the glass when the thermal expansion is measured with a thermomechanical analyzer (TMA).
本発明の光学ガラスの組成において，Ｐ2Ｏ5は，ガラス網目構造形成成分であり，ガラスに製造可能な安定性を持たせるための必須成分である。顕著な安定化効果を得るには，Ｐ2Ｏ5含有量を重量％で１８重量％以上とするのが好ましく，２０重量％以上とするのがより好ましく，２１重量％以上とするのが更に好ましい。また，光学ガラスとしての高い屈折率を得るためには，３２重量％以下とするのが好ましく，３０重量％以下とするのがより好ましい。 In the composition of the optical glass of the present invention, P 2 O 5 is a component for forming a glass network structure, and is an essential component for imparting stability that can be produced to glass. In order to obtain a remarkable stabilization effect, the P 2 O 5 content is preferably 18% by weight or more, more preferably 20% by weight or more, and more preferably 21% by weight or more. preferable. In order to obtain a high refractive index as an optical glass, it is preferably 32% by weight or less, and more preferably 30% by weight or less.
Ｂ2Ｏ3は，必須な成分ではなく，その含有量は０％であっても良いが，Ｐ2Ｏ5と同様にガラス網目構造形成成分であり，ガラスに安定性を持たせるために有効な成分であるため，例えば，１重量％以上含有させることがより好ましい。但し，光学ガラスとしての高い屈折率を得るためには，８重量％以下とするのが好ましく，６重量％以下にすることがより好ましく，５重量％以下とするのが更に好ましい。 B 2 O 3 is not an essential component, and its content may be 0%, but it is a glass network structure-forming component like P 2 O 5 and is effective for providing stability to glass. For example, it is more preferable to contain 1% by weight or more. However, in order to obtain a high refractive index as an optical glass, it is preferably 8% by weight or less, more preferably 6% by weight or less, and even more preferably 5% by weight or less.
ＧｅＯ2もＰ2Ｏ5，Ｂ2Ｏ3と同様にガラス網目構造形成成分であり，ガラスに安定性を持たせるために必須な成分である。本発明者らはまた，ＧｅＯ2を加えることで，高屈折率，低屈伏点化に大きく寄与するＢｉ2Ｏ3を更に多く含有させることが可能となり，かつ成形性を向上させることができることを見出した。ＧｅＯ2の含有量は，例えば，５重量％以上とすることが好ましく，１０重量％以上とすることがより好ましい。但し，高い屈折率を有するには，２０重量％以下とすることが好ましく，１８重量％以下にすることがより好ましく，１４重量％未満にすることが更に好ましい。 GeO 2 is also a component for forming a glass network structure like P 2 O 5 and B 2 O 3, and is an essential component for imparting stability to the glass. The present inventors have also shown that by adding GeO 2 , it becomes possible to further contain Bi 2 O 3 that greatly contributes to the formation of a high refractive index and a low yield point, and that the moldability can be improved. I found it. For example, the GeO 2 content is preferably 5% by weight or more, and more preferably 10% by weight or more. However, in order to have a high refractive index, it is preferably 20% by weight or less, more preferably 18% by weight or less, and still more preferably less than 14% by weight.
Ａｌ2Ｏ3は，本発明の目的とする，成形時の失透の発生を抑制するための必須成分である。顕著な耐失透効果を得るには，０．１重量％以上含有させるのが好ましく，０．５重量％以上含有させることがより好ましい。しかし，過剰な含有はガラスの液相温度を上げるうえに屈折率が低くなるため，含有量は１０重量％以下とするのが好ましく，８重量％以下とすることがより好ましい。また耐候性にも大きな効果を得ることができる。 Al 2 O 3 is an essential component for suppressing the occurrence of devitrification during molding, which is an object of the present invention. In order to obtain a remarkable devitrification resistance effect, the content is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more. However, excessive content raises the liquidus temperature of the glass and lowers the refractive index. Therefore, the content is preferably 10% by weight or less, and more preferably 8% by weight or less. Moreover, a big effect can be acquired also in a weather resistance.
ＺｎＯは，成形時の失透の発生を抑制し，成形性を向上させるための必須成分であり，８重量％以上含有させることが好ましく，９重量％以上含有させることがより好ましく，１０重量％以上含有させることが更に好ましい。一方，過剰な含有はガラスの液相温度を上げるため，含有量は３０重量％以下とするのが好ましく，２８重量％以下にすることがより好ましく，２６重量％以下にすることが更に好ましい。 ZnO is an essential component for suppressing the occurrence of devitrification during molding and improving moldability, and is preferably contained in an amount of 8% by weight or more, more preferably 9% by weight or more, and 10% by weight. It is still more preferable to make it contain above. On the other hand, excessive content increases the liquidus temperature of the glass, so the content is preferably 30% by weight or less, more preferably 28% by weight or less, and even more preferably 26% by weight or less.
ＴｉＯ2は，必須な成分ではなく，その含有量は０％であっても良いが，ガラスに高屈折率を付与するために有効であるため，０．１重量％以上含有させることが好ましい。但し，過剰な含有はガラスの安定性を損なうため，含有量は３重量％以下とするのが好ましい。 TiO 2 is not an essential component, and its content may be 0%. However, TiO 2 is effective for imparting a high refractive index to the glass, and is preferably contained in an amount of 0.1% by weight or more. However, since excessive content impairs the stability of the glass, the content is preferably 3% by weight or less.
Ｎｂ2Ｏ5は，ガラスに高屈折率に最も寄与する必須成分であるため，４重量％以上含有させるのが好ましい。但し，過剰な含有はガラスの安定性を損ない，また着色の原因となるため，含有量は３０重量％以下とするのが好ましく，２８重量％以下とすることがより好ましい。 Since Nb 2 O 5 is an essential component that contributes most to the high refractive index in the glass, it is preferable to contain 4% by weight or more. However, since excessive content impairs the stability of the glass and causes coloration, the content is preferably 30% by weight or less, and more preferably 28% by weight or less.
ＷＯ3は，ガラスに高屈折率低屈伏点を付与し，成形性を向上させるために有効な成分であり，例えば１重量％以上含有させるのが好ましい。但し，過剰な含有はガラスの安定性を損なうため，含有量は１２重量％以下とするのが好ましく，１０重量％以下とするのがより好ましい。 WO 3 is an effective component for imparting a high refractive index and low yield point to glass and improving formability. For example, it is preferably contained in an amount of 1% by weight or more. However, since excessive content impairs the stability of the glass, the content is preferably 12% by weight or less, and more preferably 10% by weight or less.
Ｂｉ2Ｏ3は，ガラスを高屈折率及び低屈伏点とするのに寄与する必須成分であるため，３重量％以上含有させるのが好ましい。但し，過剰な含有は成形時の成分揮発や失透を発生させやすくするため，含有量は４５重量％以下とするのが好ましく，４２重量％以下とすることがより好ましく，４０重量％以下とすることが更に好ましく，３８重量％以下とすることがいっそう好ましい。 Bi 2 O 3 is an essential component that contributes to making the glass have a high refractive index and a low yield point, and is therefore preferably contained in an amount of 3% by weight or more. However, excessive content tends to cause component volatilization and devitrification during molding, so the content is preferably 45% by weight or less, more preferably 42% by weight or less, and 40% by weight or less. More preferably, it is more preferably 38% by weight or less.
Ｒ2Ｏ成分として，Ｌｉ2Ｏ，Ｎａ2Ｏ及びＫ2Ｏの２種以上を併用することは，アルカリ混合効果によりガラスに製造可能な安定性を持たせつつ，ガラス転移点及び屈伏点を低下させるのに有効である。併用する場合には，これらの成分の含有量（それらの合計）は，例えば６重量％以上とすることができる。一方，光学ガラスとしての高い屈折率を得るためには，これらの成分の含有量を１８重量％以下にするのが好ましく，１６重量％以下とすることがより好ましい。 Using two or more of Li 2 O, Na 2 O and K 2 O as the R 2 O component gives the glass transition point and yield point while maintaining stability that can be produced in the glass by the alkali mixing effect. It is effective for lowering. When used in combination, the content of these components (the total thereof) can be, for example, 6% by weight or more. On the other hand, in order to obtain a high refractive index as an optical glass, the content of these components is preferably 18% by weight or less, and more preferably 16% by weight or less.
加えて，上記においてＬｉ2Ｏは，ガラス転移点を低下させると同時に，屈折率を保持するために有効な成分であるため，例えば，０．１重量％以上含有させることが好ましい。一方，過剰な含有はガラスの粘性を下げ，ガラスの安定性を損なうため，含有量は８重量％以下とすることが好ましく，３重量％未満とすることがより好ましい。 In addition, in the above, Li 2 O is an effective component for lowering the glass transition point and simultaneously maintaining the refractive index. On the other hand, excessive content lowers the viscosity of the glass and impairs the stability of the glass. Therefore, the content is preferably 8% by weight or less, and more preferably less than 3% by weight.
また，Ｎａ2Ｏは，ガラス転移点を低下させると同時に，ガラスの安定性を高めるために有効な成分であるため，例えば，２重量％以上含有させることが好ましく，３重量％以上含有させることがより好ましい。一方，高い屈折率を得るためには，含有量は１８重量％以下とするのが好ましく，１６重量％以下とするがより好ましい。 Further, Na 2 O is an effective component for lowering the glass transition point and at the same time improving the stability of the glass. For example, it is preferably contained in an amount of 2% by weight or more, and more preferably 3% by weight or more. Is more preferable. On the other hand, in order to obtain a high refractive index, the content is preferably 18% by weight or less, more preferably 16% by weight or less.
更に，Ｋ2Ｏの含有量は，０％であっても良いが，ガラス転移点を低下させると同時にガラスの安定性を高めるのにも有効な成分であるため，例えば，０．１重量％以上含有させることが好ましい。一方，高い屈折率を得るためには，含有量は１０重量％以下とすることが好ましい。 Further, the content of K 2 O may be 0%, but it is an effective component for lowering the glass transition point and simultaneously improving the stability of the glass. It is preferable to contain above. On the other hand, in order to obtain a high refractive index, the content is preferably 10% by weight or less.
ＢａＯは，ガラスの安定性を高め，かつ屈伏点や液相温度を低下させるために有効である。その含有量は，例えば，１．５重量％以上とするのが好ましい。但し，高屈折率を保持するためには，含有量は１５重量％以下とするのが好ましく，１４重量％以下とするのがより好ましく，１２重量％以下とするのが更に好ましい。 BaO is effective for increasing the stability of the glass and lowering the yield point and the liquidus temperature. The content is preferably 1.5% by weight or more, for example. However, in order to maintain a high refractive index, the content is preferably 15% by weight or less, more preferably 14% by weight or less, and even more preferably 12% by weight or less.
本発明のガラスは，ＭｇＯ，ＣａＯ及びＳｒＯの中から選ばれる少なくとも１種を含有する。これらの成分は，ＢａＯと共に添加したとき何れもガラスの安定性を高め，成形性の向上に寄与し，かつ屈伏点や液相温度を低下させるために有効であり，０．５重量％以上含有させるのが好ましい。但し，高屈折率を得るためには，これらの含有量の和は１０重量％以下とするのが好ましい。 The glass of the present invention contains at least one selected from MgO, CaO and SrO. These components, when added together with BaO, are effective for improving the stability of glass, improving moldability, and lowering the yield point and liquidus temperature, and contain 0.5% by weight or more. It is preferable to do so. However, in order to obtain a high refractive index, the sum of these contents is preferably 10% by weight or less.
加えて，上記においてＭｇＯは，ガラスの安定性を高め，成形性の向上に寄与し，かつ屈伏点や液相温度を低下させるために有効である。その含有量は，０．１重量％以上とするのが好ましい。但し，高屈折率を保持するためには，含有量は５重量％以下とするのが好ましく，３重量％以下とするのがより好ましい。 In addition, MgO is effective for improving the stability of glass, improving the formability, and lowering the yield point and the liquidus temperature. The content is preferably 0.1% by weight or more. However, in order to maintain a high refractive index, the content is preferably 5% by weight or less, and more preferably 3% by weight or less.
また，ＣａＯは，必須ではないが，ガラスの安定性を高め，成形性の向上に寄与し，かつ屈伏点や液相温度を低下させるために有効である。但し，高屈折率を保持するためには，含有量は５重量％以下とするのが好ましく，３重量％以下とするのがより好ましい。 In addition, CaO is not essential, but it is effective for enhancing the stability of the glass, improving the formability, and lowering the yield point and the liquidus temperature. However, in order to maintain a high refractive index, the content is preferably 5% by weight or less, and more preferably 3% by weight or less.
更に，ＳｒＯは，ガラスの安定性を高め，成形性の向上に寄与し，かつ屈伏点や液相温度を低下させるために有効である。その含有量は，０．５重量％以上とするのが好ましい。但し，高屈折率を保持するためには，含有量は５重量％以下とするのが好ましく，３重量％以下とするのがより好ましい。 Furthermore, SrO is effective for enhancing the stability of glass, contributing to improvement of formability, and lowering the yield point and the liquidus temperature. The content is preferably 0.5% by weight or more. However, in order to maintain a high refractive index, the content is preferably 5% by weight or less, and more preferably 3% by weight or less.
ＮａＦ及びＺｎＦ2は，必須ではないが，ガラスの溶融性を高め，かつ屈伏点や液相温度を低下させるために有効である。またガラスの耐候性を向上させることができる。その含有量は，１０重量％以下とするのが好ましい。 NaF and ZnF 2 are not essential, but are effective for increasing the melting property of the glass and lowering the yield point and the liquidus temperature. Moreover, the weather resistance of glass can be improved. The content is preferably 10% by weight or less.
Ｇｄ2Ｏ3，Ｙｂ2Ｏ3，ＺｒＯ2及びＴａ2Ｏ5は，必須ではないが，何れも屈折率を高める働きをするため適宜添加し得る成分である。Ｔａ2Ｏ5及びＺｒＯ2は，ガラスの安定性を高める働きも有する。このため，添加する場合これらの成分の含有量の和は，０．１重量％以上とするのが好ましく，０．５重量％以上とするのがより好ましい。その一方，これらの成分のうちＧｄ2Ｏ3，Ｙｂ2Ｏ3及びＺｒＯ2は，ガラスを高アッベ数とする方向に働き，またＴａ2Ｏ5は高価でありコスト低減に反する。従って，これらの成分の含有量の和は，３重量％以下とするのが好ましい。 Gd 2 O 3 , Yb 2 O 3 , ZrO 2 and Ta 2 O 5 are not essential, but any of them are components that can be added as appropriate because they function to increase the refractive index. Ta 2 O 5 and ZrO 2 also have a function of increasing the stability of the glass. For this reason, when added, the sum of the contents of these components is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more. On the other hand, among these components, Gd 2 O 3 , Yb 2 O 3 and ZrO 2 work to increase the glass Abbe number, and Ta 2 O 5 is expensive and goes against cost reduction. Therefore, the sum of the contents of these components is preferably 3% by weight or less.
ＴｅＯ2は，必須ではないが，ガラスの安定性を高め，かつ屈伏点や液相温度を低下させる働きを有する成分である。但し，人体に有害であるため，添加する場合その含有量は１０重量％以下とするのが好ましい。 TeO 2 is not essential, but is a component that increases the stability of the glass and lowers the yield point and the liquidus temperature. However, since it is harmful to the human body, when added, its content is preferably 10% by weight or less.
本発明の光学ガラスの製造原料については，例えば，成分Ｐ2Ｏ5のためには，ＬｉＰＯ3，ＮａＰＯ3，ＫＰＯ3，Ａｌ（ＰＯ3）3，Ｂａ（ＰＯ3）2等を用いることができ，成分Ｂ2Ｏ3のためには，Ｈ3ＢＯ3，Ｂ2Ｏ3等を用いることができ，他の成分についても，原料として各種酸化物，炭酸塩，硝酸塩等の通常の光学ガラス原料を用いることができる。それら製造原料を，上記した所定範囲の酸化物組成を達成する割合で混合し，混合物を１０００℃〜１２００℃で溶融し，清澄（ガス抜き），攪拌の各工程を経て均質化させた後，金型に流し込み徐冷することにより，無色，高屈折率で低屈伏点の，透明，均質で加工性に優れた，本発明の光学ガラスを得ることができる。 As for the raw material for producing the optical glass of the present invention, for example, LiPO 3 , NaPO 3 , KPO 3 , Al (PO 3 ) 3 , Ba (PO 3 ) 2, etc. may be used for the component P 2 O 5. For the component B 2 O 3 , H 3 BO 3 , B 2 O 3 and the like can be used, and other optical glasses such as various oxides, carbonates and nitrates are used as raw materials. Raw materials can be used. The raw materials for production are mixed at a rate that achieves the above-mentioned predetermined range of oxide composition, the mixture is melted at 1000 ° C. to 1200 ° C., homogenized through the steps of clarification (degassing) and stirring, By pouring into a mold and gradually cooling, the optical glass of the present invention can be obtained which is colorless, has a high refractive index, has a low yield point, is transparent, is homogeneous, and has excellent workability.
以下，実施例を参照して本発明を更に具体的に説明するが，本発明がそれらの実施例に限定されることは意図しない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely with reference to an Example, this invention is not intended to be limited to those Examples.
表１及び２に示した実施例及び比較例の組成となるように原料を秤量し，常法により混合物を１０００℃〜１２００℃で溶融し，清澄（ガス抜き），攪拌の各工程を経て均質化させた後，金型に流し込み徐冷することにより光学ガラスを得た。なお，比較例Ａは，特許文献１の実施例１０に記載のガラスと同一組成のもの，比較例Ｂは，特許文献２の実施例８０に記載のガラスと同一組成のもの，比較例Ｃは，特許文献３の実施例６と同一組成のものである。 The raw materials are weighed so as to have the compositions of Examples and Comparative Examples shown in Tables 1 and 2, and the mixture is melted at 1000 ° C. to 1200 ° C. by a conventional method, followed by clarification (degassing) and stirring to be homogeneous Then, it was poured into a mold and gradually cooled to obtain an optical glass. Comparative Example A has the same composition as the glass described in Example 10 of Patent Document 1, Comparative Example B has the same composition as the glass described in Example 80 of Patent Document 2, and Comparative Example C is , Which has the same composition as Example 6 of Patent Document 3.
上記ガラスの各々について，屈折率（ｎd），アッベ数（νd），屈伏点（Ａｔ）及びガラス転移点の測定を行った。また，白濁等の欠陥の有無を顕微鏡で確認した。次に，各ガラス板を賽の目状に切断加工し，複数個の同一寸法を有するカットピースを得た。さらに，複数個のカットピースの成形面を鏡面研磨し，洗浄したサンプルをプレス成形用ガラスプリフォームとした。このプレス成形用ガラスプリフォームを，貴金属系の離型膜の設けられた上コア・下コアを備えたプレス成形機に投入し，Ｎ2ガス雰囲気中にてＡｔ近傍温度まで加熱後，加圧してプレス成形し，冷却後，プレス成形品として取り出した。このプレス成型品の成形面の状態を確認すると共に，ガラスと接したコア面につき，曇りの発生等の異常の有無を目視により検査した。ここに，コア面に曇りが生じた場合，ガラスからの成分揮発が原因であり，プレス成形品の成形面に微小な荒れが生じている。加えて，コア面にそのような曇りを生じさせるガラスは，金型の反復使用につれそのようなコア面の異常を増幅させるため，プレス成形品の量産には使用できない。 For each of the glasses, the refractive index (n d ), Abbe number (ν d ), yield point (At), and glass transition point were measured. In addition, the presence of defects such as cloudiness was confirmed with a microscope. Next, each glass plate was cut into a square shape to obtain a plurality of cut pieces having the same dimensions. Furthermore, the molding surface of a plurality of cut pieces was mirror-polished, and the cleaned sample was used as a glass preform for press molding. This press-molding glass preform is put into a press molding machine having an upper core and a lower core provided with a noble metal release film, heated to a temperature close to At in an N 2 gas atmosphere, and then pressurized. The product was press-molded, and after cooling, it was taken out as a press-molded product. While confirming the state of the molding surface of this press-molded product, the core surface in contact with the glass was visually inspected for abnormalities such as fogging. Here, if the core surface becomes cloudy, it is due to component volatilization from the glass, resulting in minute roughness on the molding surface of the press-formed product. In addition, glass that causes such haze on the core surface amplifies such an abnormality of the core surface with repeated use of the mold, and therefore cannot be used for mass production of press-formed products.
屈折率（ｎd）及びアッベ数（νd）の測定は，屈折率計（カルニュー社製，ＫＰＲ−２００）を用いて行った。
ガラス転移点（Ｔｇ）及び屈伏点（Ａｔ）の測定は，長さ１５〜２０ｍｍ，直径（辺）３〜５ｍｍの棒状試料を毎分５℃の一定速度で昇温加熱しつつ，試料の伸びと温度を測定して得られた熱膨張曲線から求めた。
測定結果を表１，２に示す。
The refractive index (n d ) and Abbe number (ν d ) were measured using a refractometer (manufactured by Kalnew, KPR-200).
The glass transition point (Tg) and yield point (At) are measured by heating a rod-shaped sample having a length of 15 to 20 mm and a diameter (side) of 3 to 5 mm at a constant rate of 5 ° C. And the thermal expansion curve obtained by measuring the temperature.
The measurement results are shown in Tables 1 and 2.
表１及び２に見られるとおり，本発明の実施例のガラスは，何れも１．６５以上の高い屈折率（ｎd）を有する一方，アッベ数が低く，光学ガラスとして十分な光学恒数を有していた。また，本発明の何れのガラスも，ガラス転移点（Ｔｇ）が４００〜４９０℃の範囲内であり，Ａｔが４４０〜５５０℃という比較的低い温度範囲内にあるため，成形が容易である。更には，本発明の何れのガラスも，成形時における成形表面の白濁発生が十分に抑制されていると共に，コア面も正常であった。これらの結果から，本発明の光学ガラスが，精密モールドプレス成形による成形品の量産に好適なガラスであることがわかる。これに対し，比較例Ａのガラスは成形時に白濁を生じ，比較例Ｂのガラスは，成形時に白濁を生じることに加えて，さらに紫色の着色をも呈した。また，比較例Ｃのガラスは，成形後にコア面に曇りが生じており，成形面に微小な荒れが生じていること，及び，量産に使用できないことが明らかである。 As can be seen from Tables 1 and 2, the glasses of the examples of the present invention both have a high refractive index (n d ) of 1.65 or more, while having a low Abbe number and a sufficient optical constant as an optical glass. Had. In addition, since any glass of the present invention has a glass transition point (Tg) in the range of 400 to 490 ° C. and At in the relatively low temperature range of 440 to 550 ° C., it can be easily molded. Furthermore, in any glass of the present invention, the occurrence of white turbidity on the molding surface during molding was sufficiently suppressed, and the core surface was normal. From these results, it can be seen that the optical glass of the present invention is suitable for mass production of molded products by precision mold press molding. On the other hand, the glass of Comparative Example A produced white turbidity at the time of molding, and the glass of Comparative Example B exhibited a purple color in addition to producing white turbidity at the time of molding. In addition, it is clear that the glass of Comparative Example C is cloudy on the core surface after molding, has a minute roughness on the molding surface, and cannot be used for mass production.
本発明は，高屈折率，低アッベ数で，ガラス転移温度及びガラス屈伏点が低く，精密モールドプレス成形時に白濁を生じにくく耐失透性に優れ，非球面レンズの成形に特に適し且つ量産に適した光学ガラスを提供する。 The present invention has a high refractive index, a low Abbe number, a low glass transition temperature and a low glass yield point, is less susceptible to white turbidity during precision mold press molding, has excellent devitrification resistance, and is particularly suitable for aspherical lens molding and mass production. Provide suitable optical glass.
Claims (4)
Ｐ２Ｏ５：１８〜３２％
Ｂ２Ｏ３：０〜８％
ＧｅＯ２：５〜２０％
Ａｌ２Ｏ３：０．１〜１０％
ＺｎＯ：８〜３０％
ＴｉＯ２：０〜３％
Ｎｂ２Ｏ５：４〜３０％
ＷＯ３：１〜１２％
Ｂｉ２Ｏ３：３〜４５％
Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ：６〜１８％
（但し，Ｌｉ２Ｏ：０．１〜８％，Ｎａ２Ｏ：２〜１６％，Ｋ２Ｏ：０〜１０％）
ＢａＯ：１．３〜１５％
ＭｇＯ＋ＣａＯ＋ＳｒＯ：０．６〜１０％
（但し，ＭｇＯ：０．１〜５％，ＣａＯ：０〜５％，ＳｒＯ：０．５〜５％）
ＮａＦ：０〜１０％
ＺｎＦ：０〜１０％
を含んでなることを特徴とする光学ガラス。 A glass composition, P 2 O 5 by weight%: 18-32%
B 2 O 3: 0~8%
GeO 2: 5~20%
Al 2 O 3 : 0.1 to 10%
ZnO: 8-30%
TiO 2: 0~3%
Nb 2 O 5 : 4-30%
WO 3: 1~12%
Bi 2 O 3 : 3 to 45%
Li 2 O + Na 2 O + K 2 O: 6~18%
(However, Li 2 O: 0.1~8%, Na 2 O: 2~ 16%, K 2 O: 0~10%)
BaO: 1.3-15%
MgO + CaO + SrO: 0.6 to 10%
(However, MgO: 0.1-5%, CaO: 0-5%, SrO: 0.5-5%)
NaF: 0 to 10%
ZnF: 0 to 10%
An optical glass comprising:
Ｇｄ２Ｏ３：０〜３％
Ｙｂ２Ｏ３：０〜３％
ＺｒＯ２ ：０〜３％
Ｔａ２Ｏ５：０〜３％
（但し，Ｇｄ２Ｏ３＋Ｙｂ２Ｏ３＋ＺｒＯ２＋Ｔａ２Ｏ５：０．１〜３％）
を更に含んでなることを特徴とする，請求項１の光学ガラス。 As a glass composition, Gd 2 O 3 by weight%: 0 to 3%
Yb 2 O 3 : 0 to 3%
ZrO 2 : 0 to 3%
Ta 2 O 5 : 0 to 3%
(However, Gd 2 O 3 + Yb 2 O 3 + ZrO 2 + Ta 2 O 5: 0.1~3%)
The optical glass of claim 1, further comprising:
Refractive index (n d) from 1.65 to 1.80, a glass transition point (Tg) of from 400 to 490 ° C., a glass deformation point (At) is four hundred forty to five hundred fifty ° C., of any one of claims 1 to 3 Optical glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007178432A JP5099890B2 (en) | 2007-07-06 | 2007-07-06 | Optical glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007178432A JP5099890B2 (en) | 2007-07-06 | 2007-07-06 | Optical glass |
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| Publication Number | Publication Date |
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| JP2009013026A JP2009013026A (en) | 2009-01-22 |
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| CN101970368A (en) | 2008-02-08 | 2011-02-09 | 日本山村硝子株式会社 | Optical glass |
| CN102292300A (en) | 2009-01-26 | 2011-12-21 | 旭硝子株式会社 | Glass composition and member having the same on substrate |
| JP5589929B2 (en) * | 2011-03-30 | 2014-09-17 | 旭硝子株式会社 | Optical glass, precision press molding preform, and optical element |
| JP6590469B2 (en) * | 2014-02-26 | 2019-10-16 | 株式会社オハラ | Optical glass, lens preform and optical element |
| JP6639074B2 (en) * | 2014-03-03 | 2020-02-05 | 株式会社オハラ | Optical glass, lens preform and optical element |
| JP6347816B2 (en) * | 2016-09-30 | 2018-06-27 | 株式会社オハラ | Optical glass, optical element, and method for producing glass molded body |
| TWI714082B (en) * | 2018-05-10 | 2020-12-21 | 日商Ｈｏｙａ股份有限公司 | Optical glass and optical components |
| CN113024107B (en) * | 2021-03-18 | 2022-04-15 | 成都光明光电股份有限公司 | High-refraction high-dispersion optical glass and optical element |
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| JPS6140839A (en) * | 1984-07-31 | 1986-02-27 | Ohara Inc | Phosphate optical glass |
| JP4471418B2 (en) * | 1999-08-20 | 2010-06-02 | 株式会社住田光学ガラス | Optical glass for precision press molding |
| JP2003238197A (en) * | 2002-02-18 | 2003-08-27 | Fuji Photo Optical Co Ltd | Optical glass for press-molded lens |
| JP4233832B2 (en) * | 2002-10-02 | 2009-03-04 | 株式会社住田光学ガラス | Optical glass for molding |
| JP3982629B2 (en) * | 2002-12-27 | 2007-09-26 | Ｈｏｙａ株式会社 | Optical glass, preform for press molding, and optical element |
| JP4166174B2 (en) * | 2004-03-05 | 2008-10-15 | Ｈｏｙａ株式会社 | Precision press molding preform manufacturing method and optical element manufacturing method |
| JP4579565B2 (en) * | 2004-03-26 | 2010-11-10 | Ｈｏｙａ株式会社 | Glass outflow nozzle, glass article manufacturing method, and optical element manufacturing method |
| JP4810901B2 (en) * | 2005-07-11 | 2011-11-09 | コニカミノルタオプト株式会社 | Optical glass and optical element |
| JP2008133148A (en) * | 2006-11-28 | 2008-06-12 | Nihon Yamamura Glass Co Ltd | Optical glass |
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