WO2000039041A1 - Optical glass - Google Patents

Optical glass Download PDF

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Publication number
WO2000039041A1
WO2000039041A1 PCT/JP1999/007214 JP9907214W WO0039041A1 WO 2000039041 A1 WO2000039041 A1 WO 2000039041A1 JP 9907214 W JP9907214 W JP 9907214W WO 0039041 A1 WO0039041 A1 WO 0039041A1
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Prior art keywords
glass
optical
component
range
optical glass
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PCT/JP1999/007214
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French (fr)
Japanese (ja)
Inventor
Mitsugu Korekawa
Original Assignee
Kabushiki Kaisha Ohara
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Application filed by Kabushiki Kaisha Ohara filed Critical Kabushiki Kaisha Ohara
Priority to JP2000590957A priority Critical patent/JP4430829B2/en
Publication of WO2000039041A1 publication Critical patent/WO2000039041A1/en

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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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

Definitions

  • the present invention relates to an optical glass, particularly to an optical glass suitable for mold press molding.
  • mold press molding has been widely used as a useful processing method for optical glass.
  • press molding in which optical elements such as lenses can be directly obtained without the need for grinding or polishing after press molding, that is, precision mold press molding, can be simplified in the manufacturing process, and its usefulness has increased in recent years. I have.
  • the yield point (A t) of the glass should be as low as possible.
  • optical glasses used for lenses and the like are required to have various optical constants.
  • a desired optical constant specifically, a refractive index (nd) of 1.47 to 1 53. It is also required that the Abbe number (d) be in the range of 60 to 68.
  • Various borosilicate crown-based or barium-crown-based glasses are known as optical glasses having such optical constants.
  • “Glass Composition Data Book, 1991” Japan Glass Products Association) Issued
  • BK Shotgrass Vuelke
  • BaLK Shotgrass Vuelke
  • the present invention has an optical constant having a refractive index (nd) of 1.47 to 1.53, an Abbe number ( ⁇ cl) of 60 to 68, and a low yield point (A t). It is an object of the present invention to provide an optical glass which has good releasability from a molding die and has excellent chemical durability. Disclosure of the invention
  • the present inventors have conducted intensive tests and researches, and as a result, have a specific composition range that is not specifically disclosed in the prior art, and have a specific composition range of S i ⁇ 2 —B 20. 3 -A 1 2 ⁇ 3 - by adding R 2 ⁇ (alkali metal oxide) based glass T I_ ⁇ 2 component and Z n 0 components, the optical glass having a property to solve the above problems is obtained And found the present invention.
  • the refractive index (nd) has an optical constant in the range of 1.47 to: L.53 and the Abbé number (le d) in the range of 60 to 68.
  • the refractive index (nd) power is 1.47 to 1.53 and the Abbe number (d) has an optical constant in the range of 60 to 68.
  • the glass composition, S I_ ⁇ 2 -B 2 ⁇ 3 - it is Z Itashita system - A 1 2 0 3 - R , 0 ( alkali metal oxide) Single T i 0 2 From, Refractive index (nd) power 1.47 ⁇ 1.53, Abbe number (vd) 60 ⁇ 68 optical constant It has a low yield point (A t), high chemical durability, and has excellent devitrification resistance and is easy to homogenize.
  • optical glass of the present invention in mass%, S I_ ⁇ 2 60 ⁇ 65%, B 2 0 3 14 ⁇
  • S i 0 2 component is an essential component as the oxide to form a glass phase, the amount of that chemical durability of the glass is deteriorated is less than 60%, the precise molding exceeds 65% A suitable low yield point cannot be obtained.
  • B 2 0 3 component is also an important component as a glass forming oxide and is an effective essential ingredient to the viscosity appropriate size at the time of melting the glass, a high melt viscosity in less than 14% It is too difficult to obtain a homogeneous glass, and if it exceeds 19%, the chemical durability deteriorates.
  • the Al 2 ⁇ 3 component is effective in improving the chemical durability of the glass and preventing the phase separation of the glass.However, if the content is less than 5%, the effect is not sufficient, and if it exceeds 9%, the glass is not effective. In addition to increasing the yield point, the viscosity of the glass during molding increases, and the devitrification resistance also deteriorates.
  • the refractive index and Abbe number within the intended range, provides a low yield point and viscosity suitable for precision mold press molding, and maintains excellent chemical durability and devitrification resistance.
  • it is preferably S i O z component B 2 0 3 component, and a l 2 ⁇ ternary if weighing is 83% or more.
  • R 0 L i 2 ⁇ component is (alkali metal oxide) component, Na 2 0 component, and K 2 0 component has the effect of lowering the yield point of the glass, to the upper direction of the melt at the time of glass production It is an important component, and in order to obtain these effects, it is preferable that the Li 2 ⁇ component, the Na 2 0 component, and the K 2 ⁇ component are contained in a total range of 11% to 16%. In order to obtain glass excellent in melting property, the total amount of these three components is more preferably in the range of 12.5 to 16%.
  • the Li 20 component is an important component that has an extremely large effect of lowering the yield point of glass. To obtain the effect while maintaining the devitrification resistance and chemical durability of glass.
  • the content should be in the range of 4 to 8%, especially in order to obtain glass excellent in moldability during mold pressing, the content should be in the range of 5.5 to 8% Is more preferable.
  • Na 2 ⁇ component should be 4% or less
  • K 2 0 component should be at 6.6 to 9%.
  • T I_ ⁇ two components, prevention of coloring due to glass source one Rarizeshiyon is a component required to have improved and desired optical constants of the chemical durability, the amount of these is less than 0.05% Effect cannot be obtained, and if it exceeds 1%, the light transmittance deteriorates, which is not preferable.
  • the Zn ⁇ component improves chemical durability and gives low yield point characteristics, It has the effect of obtaining the desired optical constant and the desired viscosity at the time of molding.However, if the amount is less than 0.1%, these effects cannot be obtained, and if the amount exceeds 4%, the devitrification resistance decreases. become.
  • S b 2 0 3 component can be optionally added as a fining agent for glass, in order to obtain the effect of this, the content is sufficient to 2%.
  • the optical glass of the present invention may contain components other than those described above as necessary for adjusting optical constants, improving glass meltability, chemical durability and devitrification resistance.
  • MgO, C A_ ⁇ , S R_ ⁇ , B aO-, up to 3% in total of components such as Z R_ ⁇ 2 and F 2 may contain.
  • the optical glass of the present invention having the above composition is prepared by mixing raw materials such as oxides, carbonates, nitrates, and hydroxides at a predetermined ratio so as to have the above composition. It can be easily manufactured by melting and defoaming at a temperature for about 2 to 4 hours, homogenizing with stirring, then putting it in a mold and slowly cooling.
  • RA RA
  • the glass powder and the platinum basket were immersed in a quartz glass round bottom flask containing 80 ml of a 0.01 N nitric acid aqueous solution.
  • the round bottom flask was heated, and the nitric acid aqueous solution was boiled for 60 minutes. Thereafter, the platinum basket was removed from the round-bottom flask, the percentage (%) of the reduced glass powder weight relative to the initial weight was calculated, and grading was performed based on the percentage. If the percentage of weight loss is less than 0.20%, the RA (P) value is 1, 2 is for 0.20 to 0.35%, and 3 is 0 for 0.35 to 0.65%. 65 to less than 1.20% is 4, and 1.20 to less than 2.20% is 5. In other words, in Table 1, the smaller the RA (P) value, the higher the acid resistance and the better the chemical durability. It indicates that.
  • the glasses of the examples (No. 1 to No. 17) and the comparative examples (No. 1 and No. 2) have oxides, carbonates, nitrates, and water so as to have the compositions shown in Table 1.
  • the mixture of oxides, etc. is put into a platinum crucible and melted and defoamed at a temperature of 1200 to 1400 ° C for 2 to 4 hours depending on the degree of solubility determined by each composition, followed by stirring and homogenization. After cooling, it was poured into a mold and slowly cooled to produce the product.
  • the resulting glass was clear and homogeneous.
  • the optical glasses of Examples No. l to No. 17 have optical constants in the range of refractive index (nd) 1.47 to 1.53, Abbe number (d) 60 to 68. It can be seen that it can be sufficiently used as an optical glass. Also, the yield point (A t) is less than 550 ° C, which is suitable for mold press molding, and the releasability from the mold is good.
  • RA (P) in Table 1 is 1 or 2, which indicates that the glass has much better acid resistance and chemical durability than the glass of Comparative Example.
  • the optical glass according to the present invention S i 0 2 -B 2 0 3 having a specific composition range - A 1 2 0 3 - R 2 0 ( alkali metal oxide) - T I_ ⁇ 2 - Z Since it is an ⁇ -based glass, it has an optical constant with a refractive index (nd) of 1.47-: L. 53, an Abbe number (d) of 60-68, and a yield point (A t). Low moldability and good releasability from the mold, making it very suitable for mold press molding for obtaining optical products, especially precision mold press molding for producing lenses and the like.

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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)

Abstract

An optical glass which is characterized as comprising, based on mass %, 60 to 65 % of SiO2, 14 to 19 % of B2O3, 5 to 9 % of Al2O3, 4 to 8 % of Li2O, 0 to 4 % of Na2O, 6.6 to 9 % of K2O (with the proviso that the sum of the amounts of Li2O, Na2O and K2O is 11 to 16 %), 0.05 to 1 % of TiO2, 0.1 to 4 % of ZnO and 0 to 2 % of Sb2O3, and having a refractive index (nd) of 1.47 to 1.53 and an Abbe value (ξd) of 60 to 68. The optical glass exhibits a low incipient deformation point and has good chemical durability.

Description

明 細 書 光学ガラス 技術分野  Description Optical glass Technical field
本発明は、 光学ガラス、 特にモールドプレス成形に適した光学ガラスに関す る。 背景技術  The present invention relates to an optical glass, particularly to an optical glass suitable for mold press molding. Background art
従来より、 モールドプレス成形は、 光学ガラスの有用な加工方法として多く 利用されている。 特に、 プレス成形後に研削や研磨を必要とせず、 直接レンズ 等の光学素子を得ることができるプレス成形、 すなわち精密モールドプレス成 形は、 製造工程を簡略化できることから、 近年、 有用性が高まっている。  Conventionally, mold press molding has been widely used as a useful processing method for optical glass. In particular, press molding, in which optical elements such as lenses can be directly obtained without the need for grinding or polishing after press molding, that is, precision mold press molding, can be simplified in the manufacturing process, and its usefulness has increased in recent years. I have.
このようなモールドプレス成形においては、 ガラスの成形温度が高温になる と、 成形型の耐久性が低下したり、 ガラスが成形型に焼き付くことによってガ ラスの型に対する離型性が悪くなる、 といった問題が生じるため、 ガラスの屈 伏点 （A t ) は、 できるだけ、 低いことが望ましい。  In such a mold press molding, when the molding temperature of the glass becomes high, the durability of the molding die is reduced, and the releasability of the glass from the mold is deteriorated by burning of the glass into the molding die. Due to problems, the yield point (A t) of the glass should be as low as possible.
一方、 レンズ等に用いられる光学ガラスは、 種々の光学定数を有するものが 求められており、 その中で、 所望の光学定数、 具体的には、 屈折率 （n d ) が 1 . 4 7〜1 . 5 3、 アッベ数 （レ d ) が 6 0 ~ 6 8の範囲を有するものも求 められている。 このような光学定数を有する光学ガラスとして、 種々の硼珪酸 クラウン系あるいはバリウムクラウン系ガラスが知られており、 たとえば、 「ガ ラス組成デ一夕ブック · 1 9 9 1年 （日本硝子製品工業会発行）」 には、 硼珪 酸クラウン系ガラスとして、 B K (ショットグラスヴエルケ社商品名） タイプ のガラスが、 またバリウムクラウン系ガラスとして B a L K (ショットグラス ヴエルケ社商品名） タイプのガラスが記載されている。 しかしながら、 これら BKタイプや B a LKタイプのガラスは、 一般に、 屈 伏点 （A t) が高く、 これらの多くは 550°Cを超え、 成形温度が高いため、 モールドプレス成形用ガラスとしては、 不適当であるという問題点がある。 上記に挙げた問題点を解決するため、 R20 (アルカリ金属酸化物） を含有す るガラスが提案されている。 たとえば、 特開平 5— 193979号公報には、On the other hand, optical glasses used for lenses and the like are required to have various optical constants. Among them, a desired optical constant, specifically, a refractive index (nd) of 1.47 to 1 53. It is also required that the Abbe number (d) be in the range of 60 to 68. Various borosilicate crown-based or barium-crown-based glasses are known as optical glasses having such optical constants. For example, “Glass Composition Data Book, 1991” (Japan Glass Products Association) Issued) includes BK (Shotgrass Vuelke) glass as a borosilicate crown glass and BaLK (Shotgrass Vuelke) glass as a barium crown glass. Has been described. However, these BK-type and BALK-type glasses generally have a high yield point (A t), and many of them exceed 550 ° C and have high molding temperatures. There is a problem that it is inappropriate. In order to solve the above problems, a glass containing R 20 (alkali metal oxide) has been proposed. For example, Japanese Patent Laid-Open No. 5-193979 discloses that
S i 02— B203— A 12〇3系の組成に R2〇 （アルカリ金属酸化物） を導入した 光学ガラスが開示されているが、 この光学ガラスは、 化学的耐久性、 特に、 耐 酸性が悪いという欠点がある。 S i 0 2 - B 2 0 3 - A 1 2 〇 to 3 based composition of R 2 〇 Although optical glass was introduced (alkali metal oxide) is disclosed, the optical glass, chemical durability, In particular, it has the disadvantage of poor acid resistance.
本発明は、 上記課題に鑑み、 屈折率 （nd) が 1. 47〜1. 53、 アッベ 数 （レ cl) が 60〜68の範囲の光学定数を有し、 屈伏点 （A t) が低く、 成 形型との離型性が良好であり、 優れた化学的耐久性を有する、 光学ガラスを提 供することを目的とする。 発明の開示  In view of the above problems, the present invention has an optical constant having a refractive index (nd) of 1.47 to 1.53, an Abbe number (ベ cl) of 60 to 68, and a low yield point (A t). It is an object of the present invention to provide an optical glass which has good releasability from a molding die and has excellent chemical durability. Disclosure of the invention
以上の課題を解決すべく、 本発明者等は、 鋭意試験研究を重ねた結果、 従来 の技術には具体的に開示されていない、 特定の組成範囲を有する、 S i〇2—B 203—A 12〇3— R2〇 （アルカリ金属酸化物） 系ガラスに T i〇2成分および Z n 0成分を添加することにより、 上記課題を解決する特性を有する光学ガラス が得られることを見出し、 本発明をなすに至った。 In order to solve the above-mentioned problems, the present inventors have conducted intensive tests and researches, and as a result, have a specific composition range that is not specifically disclosed in the prior art, and have a specific composition range of S i〇 2 —B 20. 3 -A 1 2 〇 3 - by adding R 2 〇 (alkali metal oxide) based glass T I_〇 2 component and Z n 0 components, the optical glass having a property to solve the above problems is obtained And found the present invention.
本発明に係る光学ガラスは、  Optical glass according to the present invention,
質量％で、  In mass%,
S i 02 60〜65 %、 S i 0 2 60-65%,
B203 14〜： L 9 %、 B 2 0 3 14 ~: L 9%,
A 1203 5 - 9 %, A 1 2 0 3 5-9%,
L i 20 4〜8 %、 L i 20 4-8%,
N a.,0 0〜4%、 6. 6〜9% (ただし、 L i2〇、 Na2〇、 Κ.,〇は合計で 1N a., 0 0-4%, 6. 6 to 9% (however, L i 2 〇, Na 2 〇, Κ., 〇 are 1 in total
16 %)、 16%),
T i〇2 0. 05~ 1 %, T i〇 2 0.05 ~ 1%,
Ζ ηθ 0. 4%、  Ζ ηθ 0.4%,
S b203 0〜2%、 S b 2 0 3 0-2%,
の範囲で各成分を含有し、 Contains each component in the range of
屈折率 （ n d ) が 1. 47〜 ： L . 53、 アツベ数 （レ d ) が 60〜 68の範 囲の光学定数を有することを特徴とする。  It is characterized in that the refractive index (nd) has an optical constant in the range of 1.47 to: L.53 and the Abbé number (le d) in the range of 60 to 68.
また、 本発明に係る他の光学ガラスは、 Further, other optical glass according to the present invention,
質量％で、  In mass%,
S i 0, 60〜65 %、  S i 0, 60-65%,
B203 14〜； L 9 %、 B 2 0 3 14 ~; L 9%,
A 1203 5〜9 %、 A 1 2 0 3 5~9%,
L i20 5. 5〜8%、 L i 2 0 5.5-5-8%,
NNaa22〇〇 0〜4%、 NNaa 22 〇〇 0-4%,
Κ,Ο 6. 6〜9% (ただし、 L i20、 Na2〇、 K20は合計で 12.Κ, Ο 6.6 to 9% (However, L i 20 , Na 2 〇 and K 20 are 12.
5〜 16 %)、 5-16%),
T i 02 0. 05〜： L %、 T i 0 2 0.05 .: L%,
Ζ ηθ 0. 1〜4%、  Ζηθ 0.1 ~ 4%,
S b203 0〜2%、 S b 2 0 3 0-2%,
の範囲で各成分を含有し、 Contains each component in the range of
屈折率 （nd) 力 1. 47〜1. 53、 アッベ数 （レ d) が 60〜68の範 囲の光学定数を有することを特徴とする。  The refractive index (nd) power is 1.47 to 1.53 and the Abbe number (d) has an optical constant in the range of 60 to 68.
本発明の光学ガラスによれば、 ガラス組成が、 S i〇2—B2〇3— A 1203— R,0 (アルカリ金属酸化物） 一 T i 02— Z ηθ系であることから、 屈折率 （n d) 力 1. 47〜1· 53、 アッベ数 （v d) が 60〜68の範囲の光学定数 を有し、 屈伏点 （A t) が低く、 高い化学的耐久性を有し、 加えて、 耐失透性 に優れ、 均質化しやすいガラスとなる。 発明を実施するための最良の形態 According to the optical glass of the present invention, the glass composition, S I_〇 2 -B 2 〇 3 - it is Z Itashita system - A 1 2 0 3 - R , 0 ( alkali metal oxide) Single T i 0 2 From, Refractive index (nd) power 1.47 ~ 1.53, Abbe number (vd) 60 ~ 68 optical constant It has a low yield point (A t), high chemical durability, and has excellent devitrification resistance and is easy to homogenize. BEST MODE FOR CARRYING OUT THE INVENTION
以下、 本発明について詳細に説明する。  Hereinafter, the present invention will be described in detail.
本発明の光学ガラスは、 質量％で、 S i〇2 60〜65%、 B203 14〜The optical glass of the present invention, in mass%, S I_〇 2 60~65%, B 2 0 3 14~
19 %、 A 12035〜9 %、 L i 2〇 4〜8%、 Na20 0〜4%、 K2O 6. 6〜9% (ただし、 L i 20 + N a2〇 + K2〇 1 1〜16%)、 T i〇2 0. 05〜： L %、 Zn〇 0. 1〜4%、 S b,03 0〜 2 %の範囲で各成分を含 有し、 屈折率 （nd) 力 1. 47〜1. 53、 アッベ数 （ レ d) が 60〜68 の範囲の光学定数を有するものである。 19%, A 1 2 0 3 5~9%, L i 2 〇 4~8%, Na 2 0 0~4% , K 2 O 6. 6~9% ( however, L i 2 0 + N a 2 〇 + K 2 〇 1 1 to 16%), T I_〇 2 0. 05~: L%, Zn_〇 0.1 to 4%, containing organic each component in S b, 0 3 0~ 2% range The refractive index (nd) power is 1.47 to 1.53, and the Abbe number (d) is an optical constant in the range of 60 to 68.
また、 より好ましくは、 質量％で、 S i〇2 60〜65%、 B2O3 14〜 19%、 A 1203 5〜9%、 L i 20 5. 5〜8%、 N a20 0〜4%、 KMore preferably, in mass%, S I_〇 2 60~65%, B 2 O 3 14~ 19%, A 1 2 0 3 5~9%, L i 2 0 5. 5~8%, N a 2 0 0-4%, K
20 6. 6〜9% (ただし、 L i 2〇 + N a2〇 + K20 12. 5〜： L 6%)、 T i 02 0. 05〜1 %、 ΖηΟ 0. 1〜4%、 S b203 0〜2%、 の範 囲で各成分を含有し、 屈折率 （nd) が 1. 47〜1. 53、 アッベ数 （レ d) が 60〜68の範囲の光学定数を有するものである。 2 0 6.6 to 9% (however, L i 2 〇 + Na 2 〇 + K 2 0 12.5 to: L 6%), T i 0 2 0.05 to 1%, ΖηΟ 0.1 to 4%, Sb 2 0 3 0 to 2%, each component is contained, refractive index (nd) is 1.47 to 1.53, Abbe number (d) is 60 to 68. It has an optical constant.
本発明の光学ガラスにおいて、 各成分を前記組成範囲に限定した理由は、 以 下のとおりである。  The reasons for limiting each component to the above composition range in the optical glass of the present invention are as follows.
S i 02成分は、 ガラス相を形成する酸化物として必須の成分であるが、 そ の量が 60 %未満ではガラスの化学的耐久性が劣化し、 65%を超えると精密 なモールド成形に適した低屈伏点が得られなくなる。 S i 0 2 component is an essential component as the oxide to form a glass phase, the amount of that chemical durability of the glass is deteriorated is less than 60%, the precise molding exceeds 65% A suitable low yield point cannot be obtained.
B203成分も、 ガラス形成酸化物として重要な成分であり、 また、 ガラスの 溶融時の粘度を適度な大きさとするのに有効な必須成分であるが、 14%未満 では溶融粘度が高すぎて均質なガラスを得ることが困難になり、 19%を超え ると、 化学的耐久性が劣化する。 A l 2〇3成分は、 ガラスの化学的耐久性を向上させ、 ガラスの分相を防止す るために有効であるが、 5%未満ではその効果が十分ではなく、 9%を超える とガラスの屈伏点が上昇するうえ、 ガラスの成形時の粘度が高くなり、 また、 耐失透性も悪化する。 B 2 0 3 component is also an important component as a glass forming oxide and is an effective essential ingredient to the viscosity appropriate size at the time of melting the glass, a high melt viscosity in less than 14% It is too difficult to obtain a homogeneous glass, and if it exceeds 19%, the chemical durability deteriorates. The Al 2 〇 3 component is effective in improving the chemical durability of the glass and preventing the phase separation of the glass.However, if the content is less than 5%, the effect is not sufficient, and if it exceeds 9%, the glass is not effective. In addition to increasing the yield point, the viscosity of the glass during molding increases, and the devitrification resistance also deteriorates.
また、 目的の範囲内の屈折率およびアッベ数を有し、 精密なモールドプレス 成形に適した低屈伏点および粘度が得られ、 かつ、 優れた化学的耐久性ゃ耐失 透性を維持するためには、 S i Oz成分、 B203成分、 および A l2〇3成分の合 計量が 83%以上であることが好ましい。 In addition, it has a refractive index and Abbe number within the intended range, provides a low yield point and viscosity suitable for precision mold press molding, and maintains excellent chemical durability and devitrification resistance. in it is preferably S i O z component B 2 0 3 component, and a l 2 〇 ternary if weighing is 83% or more.
R 0 (アルカリ金属酸化物） 成分である L i2〇成分、 Na20成分、 および K20成分は、 ガラスの屈伏点を下げる効果を有し、 ガラス製造時の溶融性を向 上させる重要な成分であり、 これらの効果を得るため、 L i2〇成分、 Na20 成分、 および K2〇成分を合計で、 1 1〜16%の範囲で含有することが好まし レ^ 特に溶融性に優れたガラスを得るためには、 これら 3成分の合計量を 12. 5〜16 %の範囲とすることがより好ましい。 R 0 L i 2 〇 component is (alkali metal oxide) component, Na 2 0 component, and K 2 0 component has the effect of lowering the yield point of the glass, to the upper direction of the melt at the time of glass production It is an important component, and in order to obtain these effects, it is preferable that the Li 2 〇 component, the Na 2 0 component, and the K 2 〇 component are contained in a total range of 11% to 16%. In order to obtain glass excellent in melting property, the total amount of these three components is more preferably in the range of 12.5 to 16%.
これらの成分のうち、 L i20成分は、 ガラスの屈伏点を下げる効果が極めて 大きい重要な成分であり、 ガラスの耐失透性および化学的耐久性を維持しつつ、 その効果を得るために、 含有量を 4〜 8 %の範囲とすべきであり、 特に、 モ一 ルドプレス時の成形性に優れたガラスを得るためには、 その含有量を 5. 5〜 8 %の範囲とすることがより好ましい。 Among these components, the Li 20 component is an important component that has an extremely large effect of lowering the yield point of glass. To obtain the effect while maintaining the devitrification resistance and chemical durability of glass. In addition, the content should be in the range of 4 to 8%, especially in order to obtain glass excellent in moldability during mold pressing, the content should be in the range of 5.5 to 8% Is more preferable.
また、 化学的耐久性を損なわず、 低屈伏点特性を得るために、 Na2〇成分は 4%以下とすべきであり、 K20成分は 6. 6〜9 %とするべきである。 Further, without impairing chemical durability, in order to obtain a low deformation point characteristics, Na 2 〇 component should be 4% or less, K 2 0 component should be at 6.6 to 9%.
T i〇2成分は、 ガラスのソ一ラリゼーシヨンによる着色の防止、 化学的耐 久性の向上および所望の光学定数を有するために必要な成分であるが、 その量 が 0. 05 %未満ではこれらの効果が得られず、 1 %を超えると光線透過性が 劣化するので好ましくない。 T I_〇 two components, prevention of coloring due to glass source one Rarizeshiyon is a component required to have improved and desired optical constants of the chemical durability, the amount of these is less than 0.05% Effect cannot be obtained, and if it exceeds 1%, the light transmittance deteriorates, which is not preferable.
Zn〇成分は、 化学的耐久性を向上させ、 低屈伏点特性を与えるとともに、 所望の光学定数、 および望ましい成形時の粘度が得られる効果を有するが、 そ の量が 0. 1 %未満では、 これら効果が得られず、 4%を超えると耐失透性が 低下するようになる。 The Zn〇 component improves chemical durability and gives low yield point characteristics, It has the effect of obtaining the desired optical constant and the desired viscosity at the time of molding.However, if the amount is less than 0.1%, these effects cannot be obtained, and if the amount exceeds 4%, the devitrification resistance decreases. become.
S b203成分は、 ガラスの清澄剤として任意に添加することができるが、 こ の効果を得るためには、 含有量は 2%までで十分である。 S b 2 0 3 component can be optionally added as a fining agent for glass, in order to obtain the effect of this, the content is sufficient to 2%.
さらに、 本発明の光学ガラスは、 上記以外の成分を、 光学定数の調整、 ガラ スの溶融性、 化学的耐久性および耐失透性の改善のために必要に応じて含有し ていてもよく、 たとえば、 MgO、 C a〇、 S r〇、 B aO、 Z r〇2および F2等の成分を合計で 3%まで、 含有してもよい。 Further, the optical glass of the present invention may contain components other than those described above as necessary for adjusting optical constants, improving glass meltability, chemical durability and devitrification resistance. , for example, MgO, C A_〇, S R_〇, B aO-, up to 3% in total of components such as Z R_〇 2 and F 2, may contain.
上記組成からなる本発明の光学ガラスは、 酸化物、 炭酸塩、 硝酸塩、 および 水酸化物等の原料を、 上記組成を有するように、 所定の割合で混合した後、 1 200〜 1400°Cの温度で約 2〜4時間溶融脱泡し、 撹拌均質化した後、 金 型等に铸込み、 徐冷することにより、 容易に製造することができる。  The optical glass of the present invention having the above composition is prepared by mixing raw materials such as oxides, carbonates, nitrates, and hydroxides at a predetermined ratio so as to have the above composition. It can be easily manufactured by melting and defoaming at a temperature for about 2 to 4 hours, homogenizing with stirring, then putting it in a mold and slowly cooling.
実施例 Example
以下、 本発明を実施例に基づいて説明するが、 本発明はこれら実施例に限定 されるものではない。  Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.
本発明に係る光学ガラスの実施例 （No. l〜No. 17) の組成を、 屈折 率 （nd)、 アッベ数 （レ d)、 屈伏点 （A t)、 ガラス転移点 （Tg) の測定 結果、 および化学的耐久性を示す R A (P) の数値とともに、 表 1に示した。 また、 従来例として挙げた特開平 5— 193979号公報中の実施例と同様 の組成を有するガラスを、 比較例 （No. 1、 No. 2) として挙げ、 表 1に 組成と光学定数等のデータを示した。  Measurement of the refractive index (nd), Abbe number (d), yield point (A t), and glass transition point (Tg) of the compositions of Examples (No. l to No. 17) of the optical glass according to the present invention. The results are shown in Table 1 together with the values of RA (P) indicating chemical durability. Further, glass having the same composition as the example in JP-A-5-193979, which was mentioned as a conventional example, is given as a comparative example (No. 1, No. 2), and Table 1 shows the composition and optical constants. Data are shown.
なお、 ここで、 前記 RA (P) の値は、 次のようにして求めた。 実施例 No. l〜No. 17、 比較例 No. 1および No. 2で得られたそれぞれのガラス を、 粒度 425〜600 mに粉枠し、 白金製のかごの中に、 比重グラム入れ た。 P Here, the value of RA (P) was obtained as follows. Each of the glasses obtained in Examples No. 1 to No. 17 and Comparative Examples No. 1 and No. 2 was powder-framed to a particle size of 425 to 600 m and placed in a platinum basket in a specific gravity gram. . P
次に、 前記ガラス粉末を白金かごごと、 0. 01 N硝酸水溶液 80m 1が入 つている石英ガラス製の丸底フラスコに浸した。 その状態で、 丸底フラスコを 加熱し、 硝酸水溶液を 60分間沸騰させた。 その後、 白金かごを丸底フラスコ から取り出し、 減少したガラス粉末重量の最初の重量に対する割合 （％) を算 出し、 その割合に基づいて等級付けした。 減少した重量の割合が、 0. 20% 未満である場合には RA (P) 値 1とし、 0. 20〜0. 35%未満は 2、 0. 35〜0. 65%未満は 3、 0. 65〜1. 20%未満は 4、 1. 20〜2. 20%未満は 5とし、 つまり、 表 1では RA (P) の値が小さいほど、 耐酸性 が高く、 化学的耐久性が優れていることを示している。 Next, the glass powder and the platinum basket were immersed in a quartz glass round bottom flask containing 80 ml of a 0.01 N nitric acid aqueous solution. In this state, the round bottom flask was heated, and the nitric acid aqueous solution was boiled for 60 minutes. Thereafter, the platinum basket was removed from the round-bottom flask, the percentage (%) of the reduced glass powder weight relative to the initial weight was calculated, and grading was performed based on the percentage. If the percentage of weight loss is less than 0.20%, the RA (P) value is 1, 2 is for 0.20 to 0.35%, and 3 is 0 for 0.35 to 0.65%. 65 to less than 1.20% is 4, and 1.20 to less than 2.20% is 5. In other words, in Table 1, the smaller the RA (P) value, the higher the acid resistance and the better the chemical durability. It indicates that.
実施例 （No. l〜No. 17) と、 比較例 （No. 1、 No. 2) の各ガ ラスは、 表 1中の組成になるように、 酸化物、 炭酸塩、 硝酸塩、 および水酸化 物等を混合したものを、 白金坩堝に投入し、 それぞれの組成によって決まる溶 融性の程度に応じて、 1200〜1400°Cの温度で、 2〜4時間溶融脱泡し、 撹拌 ·均質化した後、 金型に流し、 徐冷することにより、 製造した。  The glasses of the examples (No. 1 to No. 17) and the comparative examples (No. 1 and No. 2) have oxides, carbonates, nitrates, and water so as to have the compositions shown in Table 1. The mixture of oxides, etc. is put into a platinum crucible and melted and defoamed at a temperature of 1200 to 1400 ° C for 2 to 4 hours depending on the degree of solubility determined by each composition, followed by stirring and homogenization. After cooling, it was poured into a mold and slowly cooled to produce the product.
得られたガラスは、 透明で均質なものであった。 The resulting glass was clear and homogeneous.
実施例 比較例Example Comparative example
No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 2 ガラス組成 （質量％) No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 2 Glass composition (% by mass)
Si02 60.5 63.0 63.0 62.5 62.0 60.0 64.0 61.0 61.4 62.0 62.0 64.0 61.0 62. 1 62.0 62.45 62.30 45.5 41.7Si0 2 60.5 63.0 63.0 62.5 62.0 60.0 64.0 61.0 61.4 62.0 62.0 64.0 61.0 62.1 62.0 62.45 62.30 45.5 41.7
B2O3 18.0 14.0 16.3 16.0 16.7 16.5 16.0 16.7 17.0 17.0 15.9 15.0 16.2 16.5 17.0 16.03 16. 10 38.0 36.4B2O3 18.0 14.0 16.3 16.0 16.7 16.5 16.0 16.7 17.0 17.0 15.9 15.0 16.2 16.5 17.0 16.03 16.10 38.0 36.4
Al203 7.0 6.0 5.0 7.2 8.0 7.2 5.5 6.0 9.0 6.0 7.0 6.0 6.0 7.0 6.7 7.22 7.25 6.5 15.5Al 2 0 3 7.0 6.0 5.0 7.2 8.0 7.2 5.5 6.0 9.0 6.0 7.0 6.0 6.0 7.0 6.7 7.22 7.25 6.5 15.5
Li 20 6.0 7.0 5.5 6.0 5.05 4.0 4.0 4.0 4.0 4.0 5.0 8.0 5.0 5.7 5.0 5.98 6.00 6.0 6.4Li 2 0 6.0 7.0 5.5 6.0 5.05 4.0 4.0 4.0 4.0 4.0 5.0 8.0 5.0 5.7 5.0 5.98 6.00 6.0 6.4
Na20 1.4 2.0 0.5 3.0 0.5 2.0 1.0 3.5 2.0 0.5 1.0 0.23 0.23 4.0Na 2 0 1.4 2.0 0.5 3.0 0.5 2.0 1.0 3.5 2.0 0.5 1.0 0.23 0.23 4.0
K2O 7.0 6.6 7.0 7.0 6.6 7.0 7.0 7.0 6.8 6.6 6.8 6.6 7.0 6.6 8.5 7. 17 7.20 K2O 7.0 6.6 7.0 7.0 6.6 7.0 7.0 7.0 6.8 6.6 6.8 6.6 7.0 6.6 8.5 7.17 7.20
Ti02 0.5 0.7 0.2 0. 1 0.05 0.3 0. 1 0.3 0. 1 0.2 0.7 0. 1 0. 1 0.5 0. 1 0. 12 0. 12 Ti0 2 0.5 0.7 0.2 0.1 0.1 0.05 0.3 0.1 0.1 0.3 0.1 0.2 0.7 0.1 0.1 0.1 0.5 0.1 12 0.1
ZnO 0.5 0.8 0.7 0.5 1.3 1.5 2.4 2.3 0.2 0.4 0.2 0. 1 4.0 0.3 0.5 0.60 0.60  ZnO 0.5 0.8 0.7 0.5 1.3 1.5 2.4 2.3 0.2 0.4 0.2 0.1 4.0 0.3 0.5 0.60 0.60
Sb203 0.5 0.5 0.3 0.2 0.3 0.5 0.5 0.7 0.5 0.3 0.4 0.2 0.2 0.3 0.2 0.20 0.20 Sb 2 0 3 0.5 0.5 0.3 0.2 0.3 0.5 0.5 0.7 0.5 0.3 0.4 0.2 0.2 0.3 0.2 0.20 0.20
nd 1.5165 1.5268 1.5219 1.5174 1.5104 1.5264 1.5097 1.5085 1.5021 1.5123 1.5150 1.5287 1.5195 1.5184 1.5124 1.5163 1.5164 1.5157 1.5123 z/d 65. 1 63.9 65.7 64.3 63.4 66.8 65.5 63.6 67.2 65.7 63.8 65.0 63.4 64.4 64.7 64. 1 64.2 64.3 63.2nd 1.5165 1.5268 1.5219 1.5174 1.5104 1.5264 1.5097 1.5085 1.5021 1.5123 1.5150 1.5287 1.5195 1.5184 1.5124 1.5163 1.5164 1.5157 1.5123 z / d 65.1 63.9 65.7 64.3 63.4 66.8 65.5 63.6 67.2 65.7 63.8 65.0 63.4 64.4 64.7 64. 1 64.2 64.3 63.2
At(。c) 492 481 539 527 521 484 521 502 489 472 504 521 545 501 542 534 533 521 527At (.c) 492 481 539 527 521 484 521 502 489 472 504 521 545 501 542 534 533 521 527
Tg(°c) 454 440 492 488 485 447 480 464 459 430 466 477 499 460 503 491 490 Tg (° c) 454 440 492 488 485 447 480 464 459 430 466 477 499 460 503 491 490
RA(P) 2 1 1 2 2 2 2 2 2 2 2 1 2 2 2 2 2 4 5 RA (P) 2 1 1 2 2 2 2 2 2 2 2 1 2 2 2 2 2 4 5
上記表 1より、 実施例 No. l〜No. 17の光学ガラスは、 屈折率 （nd) 1. 47〜1. 53、 アッベ数 （レ d) 60〜 68の範囲内の光学定数を有し、 光学ガラスとして十分に利用できるものであることが分かる。 また、 屈伏点（A t) も 550°C未満であり、 モールドプレス成形用として好適であり、 成形型 との離型性も良好なものとなる。 From Table 1 above, the optical glasses of Examples No. l to No. 17 have optical constants in the range of refractive index (nd) 1.47 to 1.53, Abbe number (d) 60 to 68. It can be seen that it can be sufficiently used as an optical glass. Also, the yield point (A t) is less than 550 ° C, which is suitable for mold press molding, and the releasability from the mold is good.
また、 表 1の RA (P) の値は 1または 2であり、 比較例のガラスより一段 と優れた耐酸性を有し、 化学的耐久性に優れていることが分かる。 産業上の利用可能性  In addition, the value of RA (P) in Table 1 is 1 or 2, which indicates that the glass has much better acid resistance and chemical durability than the glass of Comparative Example. Industrial applicability
以上述べたように、 本発明に係る光学ガラスは、 特定組成範囲の S i 02-B 203— A 1203— R20 (アルカリ金属酸化物） — T i〇2— Z ηθ系のガラスで あることから、 屈折率 （nd) が 1. 47〜： L. 53、 アッベ数 （レ d) が 6 0〜68の範囲の光学定数を有し、 屈伏点 （A t) が低く、 成形型との離型性 が良好であり、 光学製品を得るためのモールドプレス成形、 特にレンズ等を製 造するための精密モールドプレス成形に大変適している。 As described above, the optical glass according to the present invention, S i 0 2 -B 2 0 3 having a specific composition range - A 1 2 0 3 - R 2 0 ( alkali metal oxide) - T I_〇 2 - Z Since it is an ηθ-based glass, it has an optical constant with a refractive index (nd) of 1.47-: L. 53, an Abbe number (d) of 60-68, and a yield point (A t). Low moldability and good releasability from the mold, making it very suitable for mold press molding for obtaining optical products, especially precision mold press molding for producing lenses and the like.
そのうえ化学的耐久性、 特に耐酸性に優れ、 また、 高い耐失透性を有し、 均 質化しやすいため、 高品質なガラスを量産するのに適している。  In addition, it has excellent chemical durability, especially acid resistance, high resistance to devitrification, and is easily homogenized, making it suitable for mass production of high quality glass.

Claims

請 求 の 範 囲 The scope of the claims
1. 質量％で、 1. In mass%,
S i 02 60〜65 %、 S i 0 2 60-65%,
B20; 14〜 19 %、 B 2 0; 14~ 19%,
A 1203 5〜9%、 A 1 2 0 3 5~9%,
L i ,0 4 8 %、  L i, 0 4 8%,
Na20 0 4%、 Na 2 0 4%,
K20 6 6〜9% (ただし、 L i2〇、 Na20、 K,〇は合計で 1 1〜1 6 %)、 K 2 0 6 6~9% (however, L i 2 〇, Na 2 0, K, 1 1~1 6% in total 〇),
Τ i 02 0. 05〜 1 %、 Τ i 0 2 0.05.1%,
ΖηΟ 0. 1〜4%、  ΖηΟ 0.1 to 4%,
S b203 0〜2%、 S b 2 0 3 0-2%,
の範囲で各成分を含有し、 Contains each component in the range of
屈折率 （ n d ) が 1. 47〜： L . 53、 アツベ数 （レ d) が 60〜 68の範 囲の光学定数を有することを特徵とする光学ガラス。  An optical glass characterized in that the refractive index (nd) has an optical constant in the range of 1.47 to: L.53 and the Abbé number (d) in the range of 60 to 68.
2. 質量％で、  2. In mass%,
S i 02 60〜65 %、 S i 0 2 60-65%,
B203 14〜； L 9 %、 B 2 0 3 14 ~; L 9%,
A 1203 5〜9%、 A 1 2 0 3 5~9%,
L i 20 5. 5〜8 %、 L i 2 0 5.5-8%,
Na.O 0 4%、  Na.O 0 4%,
K20 6 6〜9% (ただし、 L i20、 Na20、 K20は合計で 12. 5 •16%), K 2 0 6 6~9% (however, L i 2 0, Na 2 0, K 2 0 is 12. 5 • 16% in total),
T i Ο, 0 05〜 1 %、  T i Ο, 0 05-1%,
Ζ ηθ 0. 1〜4%、 S b203 0〜2%、 Ζηθ 0.1 ~ 4%, S b 2 0 3 0-2%,
の範囲で各成分を含有し、 Contains each component in the range of
屈折率 （nd) が 1. 47〜1. 53、 アッベ数 （レ d) が 60〜 68の範 囲の光学定数を有することを特徴とする光学ガラス。  An optical glass having a refractive index (nd) of 1.47 to 1.53 and an Abbe number (d) of 60 to 68.
3. S i O B203、 A 1203の合計量が質量％で、 83%以上であることを 特徴とする請求の範囲第 1項または第 2項記載の光学ガラス。 3. S i OB 2 at 0 3, A 1 2 0 3 the total amount by weight percent, claims the first term or the optical glass of the second term, wherein a is 83% or more.
PCT/JP1999/007214 1998-12-24 1999-12-22 Optical glass WO2000039041A1 (en)

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JP2019135200A (en) * 2018-02-05 2019-08-15 株式会社オハラ Optical glass
JP2022121479A (en) * 2018-02-05 2022-08-19 株式会社オハラ optical glass
TWI774910B (en) * 2018-02-05 2022-08-21 日商小原股份有限公司 The use of optical glass

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JPH06107425A (en) * 1991-04-05 1994-04-19 Ohara Inc Optical glass
JPH0848538A (en) * 1994-08-05 1996-02-20 Ohara Inc Optical glass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06107425A (en) * 1991-04-05 1994-04-19 Ohara Inc Optical glass
JPH0848538A (en) * 1994-08-05 1996-02-20 Ohara Inc Optical glass

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JP2019135200A (en) * 2018-02-05 2019-08-15 株式会社オハラ Optical glass
JP7089887B2 (en) 2018-02-05 2022-06-23 株式会社オハラ Optical glass
JP2022121479A (en) * 2018-02-05 2022-08-19 株式会社オハラ optical glass
TWI774910B (en) * 2018-02-05 2022-08-21 日商小原股份有限公司 The use of optical glass
JP7457061B2 (en) 2018-02-05 2024-03-27 株式会社オハラ optical glass

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