JP2012092016A5

JP2012092016A5 -

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Publication number: JP2012092016A5
Application number: JP2012016333A
Authority: JP
Filing date: 2012-01-30
Publication date: 2013-04-18
Anticipated expiration: 2026-03-31

Description

本発明者らは、前記目標を達成するために鋭意試験研究を重ねた結果、ＳｉＯ_２、Ｂ_２Ｏ_３、Ｌａ_２Ｏ_３を必須成分として含有させ、かつ構成成分の比率を調整することにより、−３０〜＋７０℃の平均線膨張係数αと波長５４６．１ｎｍにおける光弾性定数βの乗算α×βが１３０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下を実現する高屈折率低分散光学ガラスを、環境負荷が高い成分及び希少鉱物資源を大量に使用することなく作製し、前記目的を達成し得ることを見出し、本発明をなすに至った。その構成を以下に示す。 As a result of intensive studies and research in order to achieve the above-mentioned goals, the inventors have included SiO ₂ , B ₂ O ₃ , La ₂ O ₃ as essential components, and adjusted the ratio of the constituent components. The multiplication α × β of the average linear expansion coefficient α of −30 to + 70 ° C. and the photoelastic constant β at a wavelength of 546.1 nm realizes 130 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less. The present inventors have found that a high refractive index and low dispersion optical glass can be produced without using a large amount of components and rare mineral resources that have a high environmental load, and the above object can be achieved. The configuration is shown below.

（構成１）
−３０〜＋７０℃の平均線膨張係数αと波長５４６．１ｎｍにおける光弾性定数βの乗算α×βが１３０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下であって、酸化物基準で、ＳｉＯ_２を１．０質量％より多く１２．０質量％未満含有し、Ｂ_２Ｏ_３を８．０〜３５．０質量％含有し、かつ、質量％比ＳｉＯ_２／Ｂ_２Ｏ_３が０を超え０．６未満であり、Ｌａ_２Ｏ_３を２５．０〜５０．０質量％含有することを特徴とする光学ガラス。 (Configuration 1)
The multiplication α × β of the average linear expansion coefficient α of −30 to + 70 ° C. and the photoelastic constant β at a wavelength of 546.1 nm is 130 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less, On the oxide basis, SiO ₂ is contained in an amount of more than 1.0% and less than 12.0% by mass, B ₂ O ₃ is contained in an amount of 8.0 to 35.0% by mass, and the mass% ratio is SiO ₂ / B. ₂ O ₃ is more than 0 and less than 0.6, and contains 25.0 to 50.0% by mass of La ₂ O ₃ .

（構成５）
構成１〜４のいずれか一項に記載のガラスであって、−３０〜＋７０℃の平均線膨張係数αと波長５４６．１ｎｍにおける光弾性定数βの乗算α×βが１００×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下であることを特徴とする光学ガラス。 (Configuration 5)
The glass according to any one of Structures 1 to 4, wherein the multiplication α × β of an average linear expansion coefficient α of −30 to + 70 ° C. and a photoelastic constant β at a wavelength of 546.1 nm is 100 × 10 ⁻¹² ° C. ^-1 * nm * cm < ^-1 ^> * Pa < ^-1 > or less, The optical glass characterized by the above-mentioned.

（構成６）
構成１〜５のいずれか一項に記載のガラスであって、−３０〜＋７０℃の平均線膨張係数αと波長５４６．１ｎｍにおける光弾性定数βの乗算α×βが９０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下であることを特徴とする光学ガラス。 (Configuration 6)
It is glass as described in any one of the structures 1-5, Comprising: The multiplication (alpha) * (beta) of the average linear expansion coefficient (alpha) of -30- + 70 degreeC and the photoelastic constant (beta) in wavelength 546.1nm is 90 * 10 < ^-12 > degreeC. ^-1 * nm * cm < ^-1 ^> * Pa < ^-1 > or less, The optical glass characterized by the above-mentioned.

（構成１３）
酸化物基準で
ＳｉＯ_２を１．０質量％より多く１０．０質量％未満、
Ｂ_２Ｏ_３を１５．０〜２８．０質量％、
Ｌａ_２Ｏ_３を２８．０〜３５．０質量％、
Ｇｄ_２Ｏ_３を２５．０〜３５．０質量％、
ＺｒＯ_２を５．０〜９．０質量％、及び
ＺｎＯを０．１〜２．０質量％未満、並びに
Ｔａ_２Ｏ_５を０．０〜６．０質量％、及び／又は
Ｎｂ_２Ｏ_５を０．０〜５．０質量％、及び／又は
Ｓｂ_２Ｏ_３を０．０〜１．０質量％、及び／又は
Ａｌ_２Ｏ_３を０．０〜１．０質量％未満
を含有するガラスであって、かつ、ＺｒＯ_２＋Ｎｂ_２Ｏ_５の合計が５．０質量％を超え１３．０質量％未満であり、屈折率(ｎｄ)が１．７８〜１．８３、アッベ数(νｄ）が４４〜４８の範囲の光学恒数を有し、−３０〜＋７０℃の平均線膨張係数αと波長５４６．１ｎｍにおける光弾性定数βの乗算α×βが９０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下であることを特徴とする光学ガラス。 (Configuration 13)
More than 1.0% by weight and less than 10.0% by weight of SiO ₂ on an oxide basis,
B ₂ O ₃ of 15.0 to 28.0 wt%,
28.0 to 35.0% by mass of La ₂ O ₃ ,
Gd ₂ O ₃ of 25.0 to 35.0 wt%,
ZrO ₂ is 5.0 to 9.0% by mass, ZnO is less than 0.1 to less than 2.0% by mass, and Ta ₂ O ₅ is 0.0 to 6.0% by mass, and / or Nb ₂ O _5. 0.0-5.0% by mass and / or Sb ₂ O ₃ 0.0-1.0% by mass and / or Al ₂ O ₃ 0.0-1.0% by mass. It is glass and the total of ZrO ₂ + Nb ₂ O ₅ is more than 5.0% by mass and less than 13.0% by mass, the refractive index (nd) is 1.78-1.83, and the Abbe number (νd ) Has an optical constant in the range of 44 to 48, and the product of the average linear expansion coefficient α of −30 to + 70 ° C. and the photoelastic constant β at a wavelength of 546.1 nm is α × β is 90 × 10 ⁻¹² ° C. ⁻¹ * Nm * cm < ^-1 ^> * Pa < ^-1 > or less optical glass characterized by the above-mentioned.

本発明の光学ガラスについて説明する。
前記構成１の光学ガラスは、−３０〜＋７０℃の平均線膨張係数αと波長５４６．１ｎｍにおける光弾性定数βの乗算α×βが１３０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下であることを特徴とし、このα×βという指標は、使用環境における結像特性の変化量を示す。より具体的に説明すると、平均線膨張係数αが大きいほど、使用環境の温度変化に対して光学素子の膨張率（体積変化）が大きいことを意味するため、治具などで固定されている光学素子には、大きな熱応力が発生することを意味する。また、光弾性定数βが大きいほど、生じた熱応力によって生じる複屈折が大きいことを意味するため、すなわち、α×βがより小さいほど、使用環境における結像特性の変化が少ないことを示唆する。
なお、α×βが１３０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下であることにより、光学設計時に所望していた結増特性が、実使用環境で温度変化が生じた場合でも実現されやすいという利益がある。 The optical glass of the present invention will be described.
In the optical glass having the constitution 1, the multiplication α × β of the average linear expansion coefficient α of −30 to + 70 ° C. and the photoelastic constant β at a wavelength of 546.1 nm is 130 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × and characterized in that Pa ^-1 or less, an indication that the alpha × beta indicates the amount of change in imaging properties in the use environment. More specifically, it means that the larger the average linear expansion coefficient α, the larger the expansion coefficient (volume change) of the optical element with respect to the temperature change in the use environment. It means that a large thermal stress is generated in the element. Moreover, it means that the larger the photoelastic constant β is, the larger the birefringence caused by the generated thermal stress is, that is, the smaller α × β is, the smaller the change in imaging characteristics in the use environment is. .
In addition, when α × β is 130 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less, the increase characteristic desired at the time of optical design changes in temperature in the actual use environment. There is a benefit that it is easy to be realized.

高屈折率低分散光学ガラスの乗算α×βが１３０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下を実現するために、構成１ではＳｉＯ_２を１．０質量％より多く１２．０質量％未満含有し、Ｂ_２Ｏ_３を８．０〜３５．０質量％含有し、かつ、質量％比ＳｉＯ_２／Ｂ_２Ｏ_３が０を超え０．６未満であり、Ｌａ_２Ｏ_３を２５．０〜５０．０質量％含有することを特徴とする。 In order to realize the multiplication α × β of the high refractive index and low dispersion optical glass at 130 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less, in the configuration 1, the SiO ₂ is less than 1.0% by mass. The content is less than 12.0% by mass, B ₂ O ₃ is contained in an amount of 8.0 to 35.0% by mass, and the mass% ratio SiO ₂ / B ₂ O ₃ is more than 0 and less than 0.6, the la ₂ O _3, characterized in that it contains 25.0 to 50.0 wt%.

前記構成５及び構成６の光学ガラスにおいては、より高精度かつ高精細な用途の光学素子に利用するために、乗算α×βは、１００×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下であることが好ましく、最も好ましくは、９０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下である。 In the optical glass of the said structure 5 and the structure 6, in order to utilize for the optical element of a highly accurate and high-definition use, multiplication (alpha) * (beta) is 100 * 10 <^{-12> degreeC-} ¹ * nm * cm <^-1> *. It is preferably Pa ⁻¹ or less, and most preferably 90 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less.

前記構成１３の光学ガラスにおいては、上述した構成１〜１２の光学ガラスのうち、最も好適な光学ガラスの構成成分比の範囲を明示したものである。具体的には
ＳｉＯ_２を１．０質量％より多く１０．０質量％未満、
Ｂ_２Ｏ_３を１５．０〜２８．０質量％、
Ｌａ_２Ｏ_３を２８．０〜３５．０質量％、
Ｇｄ_２Ｏ_３を２５．０〜３５．０質量％、
ＺｒＯ_２を５．０〜９．０質量％、及び
ＺｎＯを０．１〜２．０質量％未満、並びに
Ｔａ_２Ｏ_５を０．０〜６．０質量％、及び／又は
Ｎｂ_２Ｏ_５を０．０〜５．０質量％、及び／又は
Ｓｂ_２Ｏ_３を０．０〜１．０質量％、及び／又は
Ａｌ_２Ｏ_３を０．０〜１．０質量％未満
にガラス組成を維持することにより、特に屈折率(ｎｄ)が１．７８〜１．８３、アッベ数(νｄ）が４４〜４８の範囲の光学恒数を有し、−３０〜＋７０℃の平均線膨張係数αと波長５４６．１ｎｍにおける光弾性定数βの乗算α×βが９０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１以下である光学ガラスを安定に取得できる利益がある。上述のように、構成成分とその含有量を所定の範囲の割合とすることにより、難熔融成分や希少鉱物資源の使用を最小限に抑え、環境負荷の高い成分を使用することなく、使用環境における結像特性の変化が少ない、高精度／高精細用途の光学素子を作り出すことが可能となる。 In the optical glass of the said structure 13, the range of the component ratio of the most suitable optical glass is clearly specified among the optical glasses of the structures 1-12 mentioned above. Specifically below the SiO ₂ 1.0 wt% more 10.0% by weight,
B ₂ O ₃ of 15.0 to 28.0 wt%,
28.0 to 35.0% by mass of La ₂ O ₃ ,
Gd ₂ O ₃ of 25.0 to 35.0 wt%,
ZrO ₂ is 5.0 to 9.0% by mass, ZnO is less than 0.1 to less than 2.0% by mass, and Ta ₂ O ₅ is 0.0 to 6.0% by mass, and / or Nb ₂ O _5. the 0.0 to 5.0 wt%, and / or _Sb 2 _{O 3} of 0.0 to 1.0 wt%, and / or glass composition of _Al 2 _{O 3} less than 0.0 to 1.0 wt% In particular, the refractive index (nd) has an optical constant in the range of 1.78 to 1.83, the Abbe number (νd) in the range of 44 to 48, and an average linear expansion coefficient of −30 to + 70 ° C. Multiplying α by the photoelastic constant β at a wavelength of 546.1 nm is advantageous in that an optical glass having α × β of 90 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less can be stably obtained. As mentioned above, by making the components and their contents within a specified range, the use of hardly fusible components and rare mineral resources is minimized, and the environment in which the components are used is high without using components with high environmental impact. It is possible to produce an optical element for high-precision / high-definition applications with little change in imaging characteristics.

表１〜８に示したとおり、本発明の好ましい実施例ではいずれも所望の光学恒数、乗算α×βを実現できることが分かった。一方、表９に示した比較例では、比較例Ａは、比較的小さいα×βを実現できるが、光学恒数が近い実施例３６〜３４と比較すると、質量％比ＳｉＯ_２／Ｂ_２Ｏ_３比が０．６を超えているため、平均線膨張係数αが大きくなり、乗算α×βが９０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１を超えている。また、比較例Ｂでは、光学恒数が近い実施例３０〜３２と比較すると、ＺｎＯを多く含有しているため、光弾性定数βが大きくなってしまい、乗算α×βが１００×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１超えてしまう。その他に、ＳｉＯ_２含有量が少なく、質量％比ＳｉＯ_２／Ｂ_２Ｏ_３比が０．０５未満であるため、ガラスの耐失透性が十分でなく、ガラスを鋳込む際、ほぼガラス表面全体に結晶が発生した。また、比較例Ｃでは、ＺｎＯの含有量が著しく多く、質量％比（ＺｎＯ＋Ｙ_２Ｏ_３）／Ｌａ_２Ｏ_３が０．７３３と大きいため、光弾性定数βが増大し、乗算α×βが１３０×１０^−１２℃^−１×ｎｍ×ｃｍ^−１×Ｐａ^−１を超えてしまう。 As shown in Tables 1 to 8, it has been found that all of the preferred embodiments of the present invention can realize a desired optical constant and multiplication α × β. On the other hand, in the comparative example shown in Table 9, comparative example A can realize a relatively small α × β, but the mass% ratio SiO ₂ / B ₂ O as compared with Examples 36 to 34, which have close optical constants. _{since 3} ratio is greater than 0.6, average linear expansion coefficient alpha is increased, the multiplication alpha × beta is greater than ^{^{90 × 10 -12 ℃ -1 × nm}} × cm -1 × Pa -1. Further, in Comparative Example B, compared with Examples 30 to 32 having a close optical constant, since it contains a large amount of ZnO, the photoelastic constant β is increased, and the multiplication α × β is 100 × 10 ^−12. It will exceed [deg.] C <^-1> * nm * cm < ^-1 ^> * Pa < ^-1 >. In addition, since the SiO ₂ content is low and the mass% ratio SiO ₂ / B ₂ O ₃ ratio is less than 0.05, the devitrification resistance of the glass is not sufficient. Crystals were generated throughout. In Comparative Example C, the ZnO content is remarkably high, and the mass% ratio (ZnO + Y ₂ O ₃ ) / La ₂ O ₃ is as large as 0.733. Therefore, the photoelastic constant β increases, and the multiplication α × β is exceeds ^{^{130 × 10 -12 ℃ -1 × nm}} × cm -1 × Pa -1.

Claims

The multiplication α × β of the average linear expansion coefficient α of −30 to + 70 ° C. and the photoelastic constant β at a wavelength of 546.1 nm is 90 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less, On the oxide basis, SiO ₂ is contained in an amount of more than 1.0% and less than 12.0% by mass, B ₂ O ₃ is contained in an amount of 8.0 to 35.0% by mass, and the mass% ratio is SiO ₂ / B. ₂ O ₃ is more than 0 and less than 0.6, and contains 25.0 to 50.0% by mass of La ₂ O ₃ .

The optical glass according to claim 1, wherein the optical glass has an optical constant having a refractive index (nd) of 1.75 to 2.00 and an Abbe number (νd) of 35 to 55.

A glass according to claim 1 or 2, further an oxide basis, the _Gd 2 _{O 3} 0.0 to 40.0 _wt%, a Y 2 _{O 3} from .0 to 15.0 wt%, ZrO ₂ 0.0 to 15.0 wt%, _Ta 2 _{O 5} of 0.0 to 25.0 wt%, _Nb 2 _{O 5} of 0.0 to 18.0 wt%, WO ₃ and from 0.0 to 10 An optical glass containing 0.0% by mass.

The glass according to any one of claims 1 to 3, which is based on an oxide.
0.02 to 0.1% by weight of GeO ₂
Yb ₂ O ₃ and 0.0 to 1.0 wt%,
Ga ₂ O ₃ and 0.0 to 1.0 wt%, or _Bi 2 _{O 3} contained 0.0 to 1.0 wt%,
An optical glass containing no lead compound and arsenic compound.

A glass according to any one of claims 1 to 4, on an oxide basis, the weight percent ratio _{_{_{_{(Ta 2 O 5 + Nb 2}}}} O 5 + WO 3) / (Gd 2 O 3 + Y 2 O 3) is , And more than 0.05 and less than 1.30.

It is glass as described in any one of Claims 1-5, Comprising: By the mass% display of an oxide basis,
Li ₂ O 0-5.0%,
Na ₂ O 0-5.0%,
K ₂ O 0-5.0%,
Cs ₂ O 0~5.0%,
MgO 0-5.0%,
CaO 0-5.0%,
SrO 0-5.0%,
BaO 0-5.0%,
TiO ₂ 0-3.0%,
SnO ₂ 0-3.0%,
Al ₂ O ₃ 0-3.0%,
P ₂ O ₅ 0-5.0%,
ZnO 0 to 10.0%,
Lu ₂ O ₃ 0-5.0%,
TeO ₂ 0-3.0%,
An optical glass containing Sb ₂ O _{3 0 to} 2.0% or F 0 to 3.0%.

It is glass as described in any one of Claims 1-6, Comprising: ZnO is contained less than 2.0 mass% on an oxide basis, The optical glass characterized by the above-mentioned.

The glass according to any one of claims 1 to 7, wherein Y ₂ O ₃ is contained in an amount of less than 3.5% by mass based on an oxide.

A glass according to any one of claims 1 to 8, on an oxide basis, the weight percent ratio of _{_{_{_{(ZrO 2 + Ta 2 O 5}}}} + Nb 2 O 5) / (SiO 2 + B 2 O 3), 1 Optical glass characterized by being less than 0.00.

A glass according to any one of claims 1 to 9, on an oxide _basis, the Y 2 _{O 3} and contains less than 3.5 wt%, the weight percent ratio _{_{(ZnO + Y 2 O 3)}} / La 2 O An optical glass, wherein ₃ is greater than 0 and less than 0.5, and the mass% sum ZrO ₂ + Nb ₂ O ₅ is greater than 5.0% and less than 13.0%.

On oxide basis,
More than a SiO ₂ 1.0 wt% less than 10.0 mass%,
B ₂ O ₃ of 15.0 to 28.0 wt%,
28.0 to 35.0% by mass of La ₂ O ₃ ,
Gd ₂ O ₃ of 25.0 to 35.0 wt%,
ZrO ₂ is 5.0 to 9.0% by mass, and ZnO is less than 0.1 to 2.0% by mass,
And Ta ₂ O ₅ in an amount of 0.0 to 6.0% by mass,
Nb ₂ O ₅ of 0.0 to 5.0 wt%,
A glass containing 0.0 to 1.0% by mass of Sb ₂ O ₃ or 0.0 to less than 1.0% by mass of Al ₂ O ₃ , and the total of ZrO ₂ + Nb ₂ O ₅ is It has an optical constant of more than 5.0% by mass and less than 13.0% by mass, a refractive index (nd) of 1.78 to 1.83, and an Abbe number (νd) of 44 to 48, − Multiplication α × β of an average linear expansion coefficient α of 30 to + 70 ° C. and a photoelastic constant β at a wavelength of 546.1 nm is 90 × 10 ⁻¹² ° C. ⁻¹ × nm × cm ⁻¹ × Pa ⁻¹ or less. Optical glass.

The optical element which uses the glass as described in any one of Claims 1-11 as a base material.

An optical element produced by reheat pressing the glass according to any one of claims 1 to 11.

The optical device which uses the optical element and optical substrate material which were created with the glass as described in any one of Claims 1-11.