JP4594067B2 - Optical glass for precision press molding - Google Patents
Optical glass for precision press molding Download PDFInfo
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- JP4594067B2 JP4594067B2 JP2004369651A JP2004369651A JP4594067B2 JP 4594067 B2 JP4594067 B2 JP 4594067B2 JP 2004369651 A JP2004369651 A JP 2004369651A JP 2004369651 A JP2004369651 A JP 2004369651A JP 4594067 B2 JP4594067 B2 JP 4594067B2
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- 238000000465 moulding Methods 0.000 title claims description 16
- 239000005304 optical glass Substances 0.000 title claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 239000011521 glass Substances 0.000 description 27
- 230000003287 optical effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000004017 vitrification Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 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
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
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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)
- Glass Compositions (AREA)
Description
本発明は、環境上問題となる有害成分である酸化鉛（ＰｂＯ）や酸化テルル（ＴｅＯ2 ）等を含まないＳｉＯ2 −ＫＦ−ＡｌＦ3 −ＴｉＯ2 系で、屈折率（Ｎｄ）が１．５６〜１．６２、アッベ数（νｄ）が３１．０〜３９．０、且つガラス転移点（Ｔｇ）が５００℃以下という中屈折率高分散性の光学恒数を有する精密プレス成形用光学ガラスに関する。 The present invention is a SiO 2 —KF—AlF 3 —TiO 2 system that does not contain lead oxide (PbO), tellurium oxide (TeO 2 ), etc., which are harmful components that cause environmental problems, and has a refractive index (Nd) of 1. Optical glass for precision press molding having a medium refractive index high dispersibility optical constant of 56 to 1.62, Abbe number (νd) of 31.0 to 39.0, and glass transition point (Tg) of 500 ° C. or lower. About.
近年、光学レンズ系に使用される非球面レンズや微小な光学レンズは、高精度の金型を用いたプレス成形技術によって、研磨することなく製造されることが多くなっている。しかし、プレス成形に適する金型の材質には、加工性、耐久性、量産性等の点から様々な制限がある。これはプレス成形用ガラスの物性にも制限があることを意味しており、その最も重要な物性はガラス転移点（Ｔｇ）である。例えば、５５０℃を超えるガラス転移点を有するガラスをプレス成形するということは、成形温度が６００℃を超えることになり、金型寿命に大きな影響を与え、レンズの量産性を低下させることになる。このことから、ガラス転移点のできるだけ低いプレス成形性の優れた光学ガラスの開発が要望されている。 In recent years, aspherical lenses and minute optical lenses used in optical lens systems are often manufactured without being polished by a press molding technique using a high-precision mold. However, the mold material suitable for press molding has various limitations in terms of processability, durability, mass productivity, and the like. This means that the physical properties of the glass for press molding are also limited, and the most important physical property is the glass transition point (Tg). For example, press molding a glass having a glass transition point exceeding 550 ° C. means that the molding temperature exceeds 600 ° C., which greatly affects the mold life and reduces the mass productivity of the lens. . For this reason, there is a demand for the development of an optical glass having a low glass transition point and an excellent press formability.
屈折率が１．５６〜１．６２、アッベ数３１．０〜３９．０という本発明と同等の光学恒数を有するガラスとして、ＳｉＯ2 −ＰｂＯ−Ｒ2 Ｏ（以下、Ｒはアルカリ金属を意味する）が広く知られている。これはＰｂＯを含むため環境上非常に問題である。また、特許文献１には、精密プレス成形用ガラスとしてＳｉＯ2 −Ｂ2 Ｏ3 −Ｎｂ2 Ｏ5 −Ｒ2 Ｏ−Ｆ系ガラスが開示されているが、本発明に比べＴｇが約２０〜１００℃程度高い（後記する本発明の実施例と比較例を参照）。前述したが、精密プレス成形用金型の長寿命化にはＴｇが大きく影響し、少しでも低いＴｇを有するガラスの開発が要望されている。
さらにまた、特許文献２にはＳｉＯ2 −Ｎｂ2 Ｏ5 −Ｒ2 Ｏ−Ｆ系ガラスが、特許文献３にはＳｉＯ2 −ＴｉＯ2 −Ｎｂ2 Ｏ5 −Ｒ2 Ｏ系ガラスが開示されているが、いずれも本発明とは組成の請求範囲が異なっている。
As a glass having an optical constant equivalent to that of the present invention having a refractive index of 1.56 to 1.62 and an Abbe number of 31.0 to 39.0, SiO 2 —PbO—R 2 O (hereinafter R is an alkali metal). Meaning). This is a very environmental problem because it contains PbO. In addition, Patent Document 1 discloses SiO 2 —B 2 O 3 —Nb 2 O 5 —R 2 O—F-based glass as precision press-molding glass. It is about 100 ° C. higher (see examples and comparative examples of the present invention described later). As described above, Tg has a great influence on extending the life of precision press-molding dies, and there is a demand for the development of glass having a low Tg.
Furthermore, Patent Document 2 discloses SiO 2 —Nb 2 O 5 —R 2 O—F glass, and Patent Document 3 discloses SiO 2 —TiO 2 —Nb 2 O 5 —R 2 O glass. However, the claims of the composition are different from those of the present invention.
本発明は、屈折率（Ｎｄ）が１．５６〜１．６２、アッベ数（νｄ）が３１．０〜３９．０の範囲という中屈折率高分散性の光学恒数を有し、且つガラス転移温度（Ｔｇ）が５００℃以下で量産性に優れた精密プレス成形用光学ガラスを提供することを目的とする。 The present invention has an optical constant having a medium refractive index and high dispersion having a refractive index (Nd) of 1.56 to 1.62 and an Abbe number (νd) of 31.0 to 39.0, and glass. An object of the present invention is to provide an optical glass for precision press molding having a transition temperature (Tg) of 500 ° C. or less and excellent mass productivity.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、特許文献３発明では用いていないＦ（フッ素）を導入し、また特許文献１、２発明でのＴｉＯ2 の量（０〜１５重量％）よりも多く、１５重量％を超え２８．０重量％以下とした特定組成範囲のＳｉＯ2 −ＫＦ−ＡｌＦ3 −ＴｉＯ2 系ガラスが所期の目的を達成することを見出した。 As a result of intensive studies to achieve the above object, the present inventors have introduced F (fluorine) which is not used in the invention of Patent Document 3, and the amount of TiO 2 in Patent Documents 1 and 2 (0 It was found that a SiO 2 —KF—AlF 3 —TiO 2 glass having a specific composition range of more than 15% by weight and more than 15% by weight and not more than 28.0% by weight achieves the intended purpose. .
すなわち、本発明は、ＳｉＯ2 ４２．０〜５７．０重量％、Ｂ2 Ｏ3 ０〜８．０重量％、ＮａＦ ０〜１０．０重量％、ＫＦ １０．０〜３０．０重量％、但しＮａＦ＋ＫＦとして１８．０〜３０．０重量％、ＡｌＦ3 １．０〜１０．０重量％、Ａｌ2 Ｏ3 ０〜５．０重量％、Ｎｂ2 Ｏ5 ０〜１０．０重量％、ＴｉＯ2 １５．０重量％を超え２８．０重量％以下、ＺｒＯ2 ０〜８．０重量％、ＳｒＦ2 ０〜５．０重量％、ＢａＦ2 ０〜８．０重量％の組成からなり、屈折率（Ｎｄ）が１．５６〜１．６２、アッベ数（νｄ）が３１．０〜３９．０、ガラス転移点（Ｔｇ）が５００℃以下である中屈折率高分散性の精密プレス成形用光学ガラスを提供するものである。 That is, the present invention, SiO 2 42.0 to 57.0 wt%, B 2 O 3 from 0 to 8.0 wt%, NaF 0 to 10.0 wt%, KF 10.0 to 30.0 wt%, However from 18.0 to 30.0 wt% as NaF + KF, AlF 3 1.0~10.0 wt%, Al 2 O 3 0~5.0 wt%, Nb 2 O 5 0~10.0 wt%, TiO 2 Over 15.0% by weight and less than 28.0% by weight, ZrO 2 0-8.0% by weight, SrF 2 0-5.0% by weight, BaF 2 0-8.0% by weight, refraction For precision press molding with a medium refractive index and high dispersibility having a refractive index (Nd) of 1.56 to 1.62, an Abbe number (νd) of 31.0 to 39.0, and a glass transition point (Tg) of 500 ° C. or less. An optical glass is provided.
上記の精密プレス成形用光学ガラスの好ましい範囲の組成は次のとおりである。
ＳｉＯ2 ４３．５〜５６．０重量％、Ｂ2 Ｏ3 ０〜６重量％、ＮａＦ ０〜８．０重量％、ＫＦ １２．０〜２９．０重量％、但しＮａＦ＋ＫＦとして１９．０〜２９．０重量％、ＡｌＦ3 １．５〜９．０重量％、Ａｌ2 Ｏ3 ０〜４．０重量％、Ｎｂ2 Ｏ5 ０〜８．０重量％、ＴｉＯ2 １５．０重量％を超え２７．０重量、ＺｒＯ2 ０〜７．０重量％、ＳｒＦ2 ０〜４．０重量％、ＢａＦ2 ０〜７．０重量％。
また、Ｆの元素量の合計の好ましい範囲は１０．０重量％を超え１４．０重量％以下である。
The composition of the preferable range of said optical glass for precision press molding is as follows.
SiO 2 from 43.5 to 56.0 wt%, B 2 O 3 Less than six weight percent, NaF from 0 to 8.0 wt%, KF 12.0 to 29.0 wt%, provided that the NaF + KF 19.0-29 0.0% by weight, AlF 3 1.5 to 9.0% by weight, Al 2 O 3 0 to 4.0% by weight, Nb 2 O 5 0 to 8.0% by weight, TiO 2 exceeding 15.0% by weight 27.0 wt., ZrO 2 0-7.0 wt.%, SrF 2 0-4.0 wt.%, BaF 2 0-7.0 wt.
Moreover, the preferable range of the total element amount of F is more than 10.0% by weight and not more than 14.0% by weight.
本発明によれば、ＴｉＯ2 を多量に用い、Ｆ化合物を特定組成範囲で含有させることにより、中屈折率で高分散になり、ガラス転移温度が低いので金型寿命への影響が小さく、プレス成形用レンズや複雑な形状の微小光学素子のプレス成形による製造に有用な精密プレス成形用光学ガラスを提供することができる。 According to the present invention, by using a large amount of TiO 2 and containing the F compound in a specific composition range, the medium refractive index becomes high dispersion and the glass transition temperature is low, so the influence on the mold life is small. It is possible to provide a precision press-molding optical glass useful for production of a molding lens and a micro optical element having a complicated shape by press molding.
本発明の光学ガラスの各成分を上記のように限定した理由は次のとおりである。
ＳｉＯ2 は本発明の必須成分であり、ガラスの網目構造を構成する成分である。４２．０重量％未満ではガラスができ難く、化学的耐久性が悪くなる。また、５７．０重量％を超えるとＴｇを５００℃以下に保つことが困難になる。好ましくは４３．５〜５６．０重量％である。
The reason why each component of the optical glass of the present invention is limited as described above is as follows.
SiO 2 is an essential component of the present invention and is a component constituting a glass network structure. If it is less than 42.0% by weight, it is difficult to produce glass, and chemical durability is deteriorated. On the other hand, if it exceeds 57.0% by weight, it becomes difficult to keep Tg at 500 ° C. or lower. Preferably it is 43.5-56.0 weight%.
Ｂ2 Ｏ3 は本発明の任意成分であり、ＳｉＯ2 同様ガラスの網目構造を構成する成分である。ＳｉＯ2 の一部をＢ2 Ｏ3 に置換することにより、Ｔｇを下げることができ、またガラスの溶融性を高める。８．０重量％を超えると、ガラスの化学的耐久性、耐侯性が悪くなる。好ましくは６．０重量％以下である。 B 2 O 3 is an optional component of the present invention and, like SiO 2 , is a component constituting a glass network structure. By substituting a part of SiO 2 with B 2 O 3 , Tg can be lowered and the melting property of the glass is enhanced. If it exceeds 8.0% by weight, the chemical durability and weather resistance of the glass deteriorate. Preferably it is 6.0 weight% or less.
ＫＦは本発明の必須成分であり、フッ素（Ｆ）の供給源である。また、屈折率、Ｔｇを低下させるための重要な成分である。所期の光学恒数、Ｔｇを得るためには１０．０重量％以上必要であり、３０重量％を超えるとガラス化が難しくなる。好ましくは１２．０〜２９．０重量％である。
また、ＫＦの一部、１０．０重量％までを、好ましくは８．０重量％までをＮａＦに置き換えることもできる。ＮａＦとＫＦの合計量で１８．０重量％以上含有させる必要があり、３０．０重量％を超えるとガラス化し難くなる。好ましくは１９．０〜２９．０重量％である。
KF is an essential component of the present invention and is a supply source of fluorine (F). Further, it is an important component for lowering the refractive index and Tg. In order to obtain the desired optical constant and Tg, 10.0% by weight or more is necessary, and when it exceeds 30% by weight, vitrification becomes difficult. Preferably it is 12.0-29.0 weight%.
Further, a part of KF, up to 10.0% by weight, preferably up to 8.0% by weight, can be replaced with NaF. The total amount of NaF and KF must be 18.0% by weight or more, and if it exceeds 30.0% by weight, vitrification becomes difficult. Preferably it is 19.0-29.0 weight%.
その他のＦ供給源として、本発明はＡｌＦ3 を必須成分とする。目的とする光学恒数を得るためにＡｌＦ3 が１．０重量％以上である必要があり、１０．０重量％を超えると着色が増大し、また、ガラス化し難くなる。好ましくは１．５〜９．０重量％である。 As another F supply source, the present invention contains AlF 3 as an essential component. In order to obtain a desired optical constant, AlF 3 needs to be 1.0% by weight or more. If it exceeds 10.0% by weight, coloring increases and vitrification becomes difficult. Preferably it is 1.5-9.0 weight%.
ＢａＦ2 、ＳｒＦ2 などアルカリ土類フッ化物もＦ供給源として含有することができる。ＢａＦ2 が８．０重量％を超えるとガラス化し難くなる。また、ＳｒＦ2 が５．０重量％を超えるとガラス化し難くなる。好ましくは前者が７．０重量％以下、後者が４．０重量％以下である。
本発明において、Ｆの元素量は合計で１０．０重量％を超え１４．０重量％以下であることが好ましい。
Alkaline earth fluorides such as BaF 2 and SrF 2 can also be contained as the F supply source. When BaF 2 exceeds 8.0% by weight, vitrification becomes difficult. Further, it becomes difficult to vitrify the SrF 2 exceeds 5.0 wt%. Preferably, the former is 7.0% by weight or less, and the latter is 4.0% by weight or less.
In the present invention, the total amount of F elements is preferably more than 10.0% by weight and not more than 14.0% by weight.
Ａｌ2 Ｏ3 は本発明の任意成分であり、屈折率を下げ、耐候性を向上させる成分である。ただし、５．０重量％を超えると、Ｔｇを５００℃以下に保つことが困難になる。好ましくは４．０重量％以下である。 Al 2 O 3 is an optional component of the present invention, and is a component that lowers the refractive index and improves the weather resistance. However, if it exceeds 5.0% by weight, it becomes difficult to keep Tg at 500 ° C. or lower. Preferably it is 4.0 weight% or less.
Ｎｂ2 Ｏ5 は本発明の任意成分であり、高分散化させる成分である。しかし、１０．０重量％を超えると高屈折率になるため好ましくない。好ましくは８．０重量％以下である。 Nb 2 O 5 is an optional component of the present invention and is a component to be highly dispersed. However, if it exceeds 10.0% by weight, a high refractive index is not preferable. Preferably it is 8.0 weight% or less.
ＴｉＯ2 は本発明の必須成分であり、屈折率を比較的上げることなく、高分散化させ得る成分である。また、ＴｉＯ2 は一般的に耐候性を向上する。１５．０重量％以下では本発明の目的とするアッベ数が得難く、２８．０重量％を超えると溶融が困難になり、また、着色が増大する。好ましくは１５．０重量％を超え２７．０重量％以下である。 TiO 2 is an essential component of the present invention and can be highly dispersed without relatively increasing the refractive index. TiO 2 generally improves the weather resistance. If it is 15.0% by weight or less, it is difficult to obtain the target Abbe number of the present invention, and if it exceeds 28.0% by weight, melting becomes difficult, and coloring increases. Preferably it is more than 15.0% by weight and 27.0% by weight or less.
ＺｒＯ2 は本発明の任意成分であり、耐候性を上げる成分である。８．０重量％を超えるとＴｇを５００℃以下に保つことが困難になる。好ましくは７．０重量％以下である。 ZrO 2 is an optional component of the present invention and is a component that increases weather resistance. If it exceeds 8.0% by weight, it will be difficult to keep Tg at 500 ° C. or lower. Preferably it is 7.0 weight% or less.
本発明は上記以外のガラス成分として、基本的な光学恒数に影響を及ぼさない範囲で、ガラス製造上一般的に用いられる化合物を添加物として含有しても差し支えない。例えば、Ｃａ、Ｓｒ、Ｂａ、Ｇａ、Ｉｎ、Ｙ、Ｌａ、Ｇｄ、Ｙｂなどの金属酸化物、ハロゲン化合物を含有することができる。Ｓｒ、Ｂａのフッ化物の含有量については上記のとおり各々５．０重量％以下、８．０重量％以下とする。 In the present invention, as a glass component other than the above, a compound generally used in glass production may be added as an additive as long as the basic optical constant is not affected. For example, metal oxides such as Ca, Sr, Ba, Ga, In, Y, La, Gd, and Yb, and halogen compounds can be contained. The Sr and Ba fluoride contents are 5.0% by weight or less and 8.0% by weight or less as described above.
本発明の光学ガラスは、各成分の原料として各々に相当する酸化物、水酸化物、炭酸塩、硝酸塩、ハロゲン化物等を用い、ガラス化した後に目的とするガラス組成の割合となるように秤量し、充分混合してガラス調合原料として白金製坩堝に投入し、１０００℃〜１４００℃で溶融し、白金製攪拌棒にて適時攪拌して清澄、均質化してから適当な温度で予熱した金型内に鋳込んだ後、徐冷して製造することができる。なお、脱泡剤として少量のＳｂ2 Ｏ3 を加えてもよい。 The optical glass of the present invention uses an oxide, hydroxide, carbonate, nitrate, halide or the like corresponding to each component as a raw material for each component, and is weighed so as to have a desired glass composition ratio after vitrification. And then mixed into a platinum crucible as a glass preparation raw material, melted at 1000 ° C to 1400 ° C, stirred with a platinum stirrer in a timely manner, clarified and homogenized, and preheated at an appropriate temperature. It can be manufactured by slow cooling after casting in. A small amount of Sb 2 O 3 may be added as a defoaming agent.
以下、実施例を挙げて本発明の光学ガラスを具体的に説明するが、本発明はこれに限定されるものではない。
〔実施例１〜１３〕
本発明の光学ガラスの実施例１〜１３の成分組成（重量％）、及びその光学恒数（ｎｄ、νｄ）と転移温度（Ｔｇ）を表１に示した。転移温度（Ｔｇ）は熱膨張測定器を用いて、毎分５℃で昇温した結果を示した。また本実施例の光学ガラスは表１にある各実施例の組成割合となるようにガラス原料を所定の重量に調合し、十分混合した後に白金製坩堝に投入して１０００〜１４００℃で溶融し、適時攪拌して均質化を図り、その融液を金型に鋳込んだ後、徐冷し得られたものである。
Hereinafter, although an example is given and the optical glass of this invention is demonstrated concretely, this invention is not limited to this.
[Examples 1 to 13]
Table 1 shows component compositions (% by weight) of Examples 1 to 13 of the optical glass of the present invention, optical constants (nd, νd), and transition temperature (Tg). The transition temperature (Tg) shows the result of increasing the temperature at 5 ° C. per minute using a thermal expansion measuring device. In addition, the optical glass of this example was prepared by mixing glass raw materials in a predetermined weight so that the composition ratio of each example shown in Table 1 was obtained, and after thoroughly mixing, it was put into a platinum crucible and melted at 1000 to 1400 ° C. Then, the mixture was homogenized by timely stirring, and the melt was cast into a mold and then slowly cooled.
〔比較例１及び２〕
表２に特許文献１発明の実施例３，実施例５のガラスについて、組成、屈折率（ｎｄ）、アッベ数（νｄ）、転移温度（Ｔｇ）を、特許文献１の記載に従って記したものである（比較例１及び２）。
[Comparative Examples 1 and 2]
Table 2 describes the composition, refractive index (nd), Abbe number (νd), and transition temperature (Tg) of the glass of Examples 3 and 5 of the invention of Patent Document 1 according to the description of Patent Document 1. (Comparative Examples 1 and 2).
表１、表２を比較すると、比較例１及び２のガラスは転移温度（Ｔｇ）が５４５℃、５２０℃と５００℃を超えている。これに対し本発明の実施例１〜１３のガラスはＴｇが４２６〜４９９℃と５００℃以下で、比較例より２０〜１２０℃程低いことがわかる。また、本発明ガラスはＴｉＯ2 を多量に含有させ、Ｆ化合物を特定の組成範囲とすることにより、屈折率が１．５６７０３（実施例９）〜１．６１０５４（実施例１３）で、アッベ数は３２．２（実施例１３）〜３７．６（実施例１０）と中屈折率高分散性という所期の光学恒数を得ていることがわかる。 When Table 1 and Table 2 are compared, the glasses of Comparative Examples 1 and 2 have transition temperatures (Tg) of 545 ° C., 520 ° C., and 500 ° C. or higher. In contrast, the glasses of Examples 1 to 13 of the present invention have Tg of 426 to 499 ° C. and 500 ° C. or less, which is 20 to 120 ° C. lower than the comparative example. In addition, the glass of the present invention contains a large amount of TiO 2 and the F compound in a specific composition range, whereby the refractive index is 1.56703 (Example 9) to 1.61054 (Example 13), and the Abbe number. It can be seen that 32.2 (Example 13) to 37.6 (Example 10) and a desired optical constant of medium refractive index and high dispersibility are obtained.
図１は上記の実施例１〜１３で得られた本発明ガラスの光学恒数について、アッベ数をｘ軸、屈折率をｙ軸としてプロットしたグラフである。
本発明ガラスの特に好ましい実施形態によるガラスは、その光学恒数が、図１において下記の式で示される４本の直線 I〜IV ｙ＝１．５６ ・・・直線 I
ｙ＝−０．０２ｘ＋２．３４ ・・・直線 II
ｙ＝１．６２ ・・・直線 III
ｙ＝−０．０１５ｘ＋２．０８５ ・・・直線 IV
で囲まれる領域Ａの範囲内にあることを示している。
FIG. 1 is a graph in which the Abbe number is plotted on the x-axis and the refractive index is plotted on the y-axis for the optical constants of the glasses of the present invention obtained in Examples 1 to 13 above.
The glass according to a particularly preferred embodiment of the glass of the present invention has an optical constant of four straight lines I to IV y = 1.56 represented by the following formula in FIG.
y = −0.02x + 2.34 ・ ・ ・ Line II
y = 1.62 ... straight line III
y = -0.015x + 2.085 ... straight line IV
It is within the range of area A surrounded by.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05262534A (en) * | 1992-03-17 | 1993-10-12 | Ohara Inc | High-dispersion optical glass |
| JP2002114536A (en) * | 2000-10-02 | 2002-04-16 | Sumita Optical Glass Inc | Ultraviolet ray resistant glass |
| JP2002356348A (en) * | 2001-03-28 | 2002-12-13 | Sumita Optical Glass Inc | Optical glass for forming mold lens |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05262534A (en) * | 1992-03-17 | 1993-10-12 | Ohara Inc | High-dispersion optical glass |
| JP2002114536A (en) * | 2000-10-02 | 2002-04-16 | Sumita Optical Glass Inc | Ultraviolet ray resistant glass |
| JP2002356348A (en) * | 2001-03-28 | 2002-12-13 | Sumita Optical Glass Inc | Optical glass for forming mold lens |
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