JPH0416526A - Lightweight fluorophosphate optical glass - Google Patents
Lightweight fluorophosphate optical glassInfo
- Publication number
- JPH0416526A JPH0416526A JP2117386A JP11738690A JPH0416526A JP H0416526 A JPH0416526 A JP H0416526A JP 2117386 A JP2117386 A JP 2117386A JP 11738690 A JP11738690 A JP 11738690A JP H0416526 A JPH0416526 A JP H0416526A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- mol
- optical glass
- lightweight
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005304 optical glass Substances 0.000 title claims abstract description 16
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 title claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 230000005484 gravity Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- -1 oxygen ion Chemical class 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000004031 devitrification Methods 0.000 abstract description 17
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910001637 strontium fluoride Inorganic materials 0.000 abstract description 2
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 abstract description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 abstract 2
- 229910002319 LaF3 Inorganic materials 0.000 abstract 1
- 229910021180 PF3 Inorganic materials 0.000 abstract 1
- 230000002159 abnormal effect Effects 0.000 abstract 1
- 229910001632 barium fluoride Inorganic materials 0.000 abstract 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 abstract 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 abstract 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000002547 anomalous effect Effects 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、比重３．６以下の軽量弗燐酸塩光学ガラスに
関するものであり、その光学恒数は、屈折率ｎｉ ＝１
．４２〜１．５０、ア・７ベ数ν４＝８０〜９７に及ぶ
。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a lightweight fluorophosphate optical glass with a specific gravity of 3.6 or less, whose optical constant is a refractive index ni = 1
．． 42 to 1.50, A.7be number ν4 = 80 to 97.
本発明の弗燐酸塩光学ガラスは、異常部分分散性を有し
、レンズ設計に際して二次スペクトルの修正を可能にす
るところから、光学系に極めて重要で、かつ軽量である
ところから、大口径写真レンズ、テレビカメラ用レンズ
部品としての利用価値が高い。The fluorophosphate optical glass of the present invention has anomalous partial dispersion, which is extremely important for optical systems because it makes it possible to modify the secondary spectrum when designing lenses, and because it is lightweight, it is suitable for large-diameter photography. Highly useful as lenses and lens parts for television cameras.
異常部分分散性を有し、かつ軽量な低分散光学材料とし
て、従来からの結晶性の蛍石（ＣａＦｚ）が知られてお
り、その光学恒数及び比重Ｓｇ、は次の通りである。Crystalline fluorite (CaFz) is conventionally known as a lightweight, low-dispersion optical material that has anomalous partial dispersion, and its optical constants and specific gravity Sg are as follows.
ｎ、 ＝１．４３３８
ν、 ＝９５．３
Ｓｇ、 ＝３．１８
しかし蛍石は、へき開性があり、脆いため、加工性が悪
いという欠点がある。さらに近年、レンズの大口径化に
対する要求が高まりつつある中で、均質な大きな結晶塊
を得難く、非常に高価なものにしていた。n, =1.4338 ν, =95.3 Sg, =3.18 However, fluorite has the disadvantage of poor workability because it is cleavable and brittle. Furthermore, in recent years, as the demand for larger diameter lenses has increased, it has become difficult to obtain large homogeneous crystal blocks, making them extremely expensive.
そこで、蛍石に代わる光学材料として、様々な弗燐酸塩
光学ガラスが開発され（例えば、特公昭５４−３４７６
８号公報、特開平１−２７０５３７号公報、特公昭５７
−４４６１８号参照）、市販品として硝種名ＦＫＯＩ、
ＰＣＤＩ、ＦＫＯ２、ＦＣＤＩＯ、ＣａＦＫ９５が入
手できる。Therefore, various fluorophosphate optical glasses were developed as optical materials to replace fluorite (for example, Japanese Patent Publication No. 54-3476
Publication No. 8, Japanese Patent Publication No. 1-270537, Japanese Patent Publication No. 1983
-44618), glass type name FKOI as a commercial product,
PCDI, FKO2, FCDIO, and CaFK95 are available.
しかしながら、従来のガラスは、蛍石に比べて比重が大
きく、レンズの大口径化に伴う光学機器用光学材料とし
て使用するには望ましくなかった。However, conventional glass has a higher specific gravity than fluorite, making it undesirable for use as an optical material for optical equipment as lenses become larger in diameter.
また、特公昭５７−４４６１８号の発明は、失透に対す
る安定性を高め、成形時の粘性を上げるために、Ｓｉを
必須成分として添加している。しかし、ガラス中にＳｉ
が含まれると、大型のレンズ形状に加工するプレス工程
で、Ｓｉを結晶核とした失透が発生しやすく、大口径レ
ンズを得ることは非常に困難であった。Further, in the invention of Japanese Patent Publication No. 57-44618, Si is added as an essential component in order to improve stability against devitrification and increase viscosity during molding. However, Si in the glass
If such a material is included, devitrification using Si as a crystal nucleus is likely to occur during the pressing process for forming a large lens shape, making it extremely difficult to obtain a large diameter lens.
従って、本発明の目的は、上述のごとき問題点を克服し
、比重が３．６以下にあり、屈折率ｎ４が１．４２〜１
．５０、アツベ数ν４が８０〜９７の範囲にあり、異常
部分分散性を有し、加工性に優れ、大口径レンズを得る
際にも失透に対して安定で、工業的規模での生産が可能
な、軽量弗燐酸塩光学ガラスを提供することにある。Therefore, an object of the present invention is to overcome the above-mentioned problems, have a specific gravity of 3.6 or less, and a refractive index n4 of 1.42 to 1.
．． 50, has an Atsube number ν4 in the range of 80 to 97, has anomalous partial dispersion, is excellent in processability, is stable against devitrification even when obtaining large diameter lenses, and is suitable for industrial scale production. Our goal is to provide lightweight fluorophosphate optical glasses.
そこで、本発明（請求項第１項）は、
「 陰イオンとして弗素イオンＦ−と、酸素イオン０！
−とを含み、ガラス中の陽イオンを弗化物として表記し
た場合、モル％で、
ｐｐ、 ５、ｏ〜３０．０％
ＡｌＦ□ １９．０〜４０．０％
ＣａＦｚ ２８．０〜５６．０％
ＭｇＦ、 ０〜２０．０％
ＳｒＦ、 ０〜 ９．０％
ＢａＦｚ ０〜１８．０％
ＺｎＦｚ ０〜１０．０％
ＮａＦ ０〜 ４．０％
ＫＦ ０〜 ４，０％
ＹＦ３ ０〜１３．０％
ＬａＦ＝ ｏ〜 ７．０％
の組成範囲を有し、ガラス中におけるＦ−／Ｏ２（酸素
イオン数に対する弗素イオン数の比）が、１．４〜１３
．０の範囲にあり、比重が３．６以下であることを特徴
とする軽量弗燐酸塩光学ガラス」を提供する。Therefore, the present invention (Claim 1) provides: ``Fluorine ion F- as anion and oxygen ion 0!
- and when the cation in the glass is expressed as fluoride, in mol%, pp, 5, o ~ 30.0% AlF□ 19.0 ~ 40.0% CaFz 28.0 ~ 56.0 % MgF, 0-20.0% SrF, 0-9.0% BaFz 0-18.0% ZnFz 0-10.0% NaF 0-4.0% KF 0-4.0% YF3 0-13. It has a composition range of 0% LaF = o to 7.0%, and F-/O2 (ratio of the number of fluorine ions to the number of oxygen ions) in the glass is 1.4 to 13.
．． 0 and a specific gravity of 3.6 or less.
本発明のガラスは、本質的には、Ｐ−＾１−ＣａＦ−０
系ガラスから構成されているが、本発明は、従来の弗燐
酸塩光学ガラスよりも、Ｃａを多量に含むガラス化領域
を見いだすことによって、目的とする軽量ガラスを得た
点に特徴がある。The glass of the present invention essentially consists of P-^1-CaF-0
However, the present invention is characterized in that the target lightweight glass was obtained by finding a vitrified region containing a larger amount of Ca than conventional fluorophosphate optical glasses.
以下に、各成分の組成範囲を決めた理由を述べる。The reasons for determining the composition range of each component will be described below.
ガラス中に、燐酸成分、たとえばＰ２Ｏ，が存在すると
、ＰＪｓはガラス形成酸化物として働き、構造の安定化
すなわち失透に対する安定性を増す。When a phosphoric acid component, such as P2O, is present in the glass, PJs acts as a glass-forming oxide and increases the stabilization of the structure, ie, the stability against devitrification.
ＰＦ、として５．０モル％未満ではその効果が得られず
、３０，０モル％を越えると、分散が大きくなり、目的
とする光学慟数が得られない。If the amount of PF is less than 5.0 mol%, the effect cannot be obtained, and if it exceeds 30.0 mol%, the dispersion becomes large and the desired optical density cannot be obtained.
ＡＩＦｆｆは、失透析出温度を下げ、ガラスを安定化さ
せる効果が大きく、さらに化学的耐久性を高めるため、
１９．０〜４０．０モル％の範囲で必須である。AIFff has a great effect of lowering the dialysis temperature and stabilizing the glass, and also increases chemical durability.
It is essential in the range of 19.0 to 40.0 mol%.
この範囲外の量では、ガラスの失透に対する安定性が得
られない。If the amount is outside this range, stability against devitrification of the glass cannot be obtained.
アルカリ土類金属の内、原子番号の小さい金属の弗化物
は、分散を小さくするとともに、比重を小さくする効果
がある。特にＣａＦｚはガラスの粘性を高める効果があ
るので必須である。その量は２８．０モル％未満では十
分な効果が得られず、逆に５６．０モル％を越えると失
透しやすくなる。Among alkaline earth metals, fluorides of metals with small atomic numbers have the effect of reducing dispersion and specific gravity. In particular, CaFz is essential because it has the effect of increasing the viscosity of glass. If the amount is less than 28.0 mol%, a sufficient effect cannot be obtained, whereas if it exceeds 56.0 mol%, devitrification tends to occur.
ガラス中における弗素イオン数と酸素イオン数の比Ｆ−
１０！−は、ガラスの分散、失透に対する安定性に大き
な影響を与える。この比が１．４未満では分散が大きく
なり過ぎ、逆に１３．０を越えると失透傾向が高まる。Ratio of the number of fluorine ions to the number of oxygen ions in glass F-
10! - has a great influence on the stability against dispersion and devitrification of the glass. If this ratio is less than 1.4, the dispersion becomes too large, and if it exceeds 13.0, the tendency to devitrify increases.
上記のごときＰ −ＡＩ −Ｃａ −Ｆ−０系で、目的
とする光学ガラスを得ることができるが、他の成分を適
量添加することによって、光学恒数範囲をさらに拡大で
き、ガラスの軽量化、また失透に対する安定性をさらに
向上させることができる。The desired optical glass can be obtained using the P -AI -Ca -F-0 system as described above, but by adding appropriate amounts of other components, the range of optical constants can be further expanded and the weight of the glass can be reduced. Moreover, the stability against devitrification can be further improved.
ＭｇＦ、を添加すると、ガラスの比重を小さくし、さら
に分散を小さくすることができる。但し、２０．０モル
％を越えると失透しやすくなる。Adding MgF can reduce the specific gravity of the glass and further reduce dispersion. However, if it exceeds 20.0 mol%, devitrification tends to occur.
ＳｒＦ２及びＢａＦｚは、失透に対する安定性を高める
効果が大きい。但し、適量を越えるとガラスの比重が大
きくなり過ぎるので、５ｒＦｚは９，０モル％以下、Ｂ
ａＦｚは１８モル％以下で用いるべきである。SrF2 and BaFz are highly effective in increasing stability against devitrification. However, if the appropriate amount is exceeded, the specific gravity of the glass will become too large, so 5rFz should be 9.0 mol% or less, B
aFz should be used at 18 mol% or less.
ＺｎＦｚを添加すると、失透に対する安定性が増す場合
がある。適量を越えて添加すると、目的の低分散が得ら
れなくなるので、１０．０モル％以下で用いるべきであ
る。Addition of ZnFz may increase stability against devitrification. If added in excess of an appropriate amount, the desired low dispersion cannot be obtained, so it should be used in an amount of 10.0 mol% or less.
アルカリ金属弗化物を添加すると、ガラスの融液温度を
下げ、ガラス化を容易にするが、適量を越えると粘性を
下げるので、均質な大口径レンズを得難くなる。そのた
め、ＮａＦ及びＫＦは、４．０モル％までなら添加して
もよいが、ＬｉＦは、大口径レンズを得るに十分な失透
に対する安定性が得られないので、添加してはならない
。Addition of an alkali metal fluoride lowers the glass melt temperature and facilitates vitrification, but if it exceeds an appropriate amount, it lowers the viscosity, making it difficult to obtain a homogeneous large-diameter lens. Therefore, NaF and KF may be added up to 4.0 mol %, but LiF must not be added because it does not provide sufficient stability against devitrification to obtain a large diameter lens.
Ｙｈ及び希土類元素の弗素物、たとえばＬａＦｉを少量
添加することによって、化学的耐久性、失透に対する安
定性の向上、さらに光学特性の拡大を図ることができる
。適量を越えて添加するとかえって失透しやすくなるの
で、ＹＦｊは１３，０モル％以下、ＬａＦ、は７．０モ
ル％以下で用いるべきである。By adding a small amount of Yh and a fluoride of a rare earth element, such as LaFi, it is possible to improve chemical durability and stability against devitrification, and further expand optical properties. If more than an appropriate amount is added, devitrification tends to occur, so YFj should be used in an amount of 13.0 mol% or less, and LaF should be used in an amount of 7.0 mol% or less.
但し、ＮｄＦ、は、ガラスを着色するので、光学ガラス
としては適当ではなく、添加してはならない。However, since NdF colors the glass, it is not suitable for optical glass and must not be added.
以上の第１の組成範囲（請求項第１項）のうち特にＰＦ
、 、ＮａＦ及びＫＰの組成範囲が、モル％で、ＰＦｓ
８．０〜３０．０％
ＮａＦ ０
ＫＦ Ｏ
であり、ガラス中におけるＦ−１０２−（＃素イオン数
に対する弗素イオン数の比）が、１．４〜９．０の範囲
にあるガラス（請求項第２項）は、成形時の粘性が高く
、大口径レンズを得る目的に適している。Among the above first composition ranges (claim 1), especially PF
, , the composition range of NaF and KP is in mol%, PFs
8.0 to 30.0% NaF 0 KFO and the F-102- (ratio of the number of fluorine ions to the number of # elementary ions) in the glass is in the range of 1.4 to 9.0 (claimed Item 2) has a high viscosity during molding and is suitable for the purpose of obtaining a large diameter lens.
更に、第２の組成範囲（請求項第２項）のうち特にＭｇ
Ｆ、及びＢａ１ｔの組成範囲が、モル％で、阿ｇＦｔ
Ｏ，５〜２０．０％
ＢａＦｚ ０〜１３．０％
であるガラス（請求項第３項）は、比重が３．５５以下
であり、より軽い。Furthermore, in the second composition range (claim 2), particularly Mg
The composition range of F and Ba1t is mol%, AgFt
Glass containing O, 5 to 20.0% and BaFz 0 to 13.0% (claim 3) has a specific gravity of 3.55 or less and is lighter.
第３の組成範囲Ｃ請求項第３項）のうち特にＡｌＦ３及
びＣａＦｚの組成範囲が、モル％で、ＡｌＦ３２０．０
〜３６．０％
ＣａＦｚ ２８．０〜４８．０％
であるガラス（請求項第４項）は、失透に対してより安
定である。In particular, the composition range of AlF3 and CaFz in the third composition range C (Claim 3) is mol% AlF320.0
-36.0% CaFz 28.0-48.0% (claim 4) is more stable against devitrification.
本発明のガラスを製造する場合、リン原料には、ＨｚＰ
ＯａやＰｔＯｓや各種金属リン酸塩を用いることができ
る０通常、アルカリ金属、アルカリ土類金属、又はアル
ミニウムのメタ燐酸塩を用いるのが良い。When producing the glass of the present invention, the phosphorus raw material contains HzP
Although Oa, PtOs, and various metal phosphates can be used, it is usually preferable to use metaphosphates of alkali metals, alkaline earth metals, or aluminum.
その他の成分については、通常、成分陽イオンを含む金
属弗化物を原料として用いるが、ガラス中におけるＦ−
／Ｏ２−が所定の範囲内において、金属酸化物、金属炭
酸塩等の酸素化合物を併用することもできる。For other components, metal fluorides containing component cations are usually used as raw materials, but F-
Oxygen compounds such as metal oxides and metal carbonates can also be used in combination within a predetermined range of /O2-.
その外、原料として、上記成分陽イオンを含む金属塩化
物、臭化物、沃化物等を少量程度併用することも可能で
ある。In addition, small amounts of metal chlorides, bromides, iodides, etc. containing the above component cations can also be used as raw materials.
また、＾５、 Ｓｂ、 Ｔｉ、 Ｐｂ、 Ｚｒ、 Ｙｂ
、 Ｇｄ、 Ｃｅ等の各金属元素を、これらの元素の弗
化物、弗素錯塩及び酸化物等を原料として添加すること
により、ガラス中にそれぞれ４モル％程度まで含有させ
てもよい、これにより、ガラスのソラリゼーションの向
上や、光学特性の多様化を図ることができる。Also, ^5, Sb, Ti, Pb, Zr, Yb
, Gd, Ce, etc., may be contained up to about 4 mol% in the glass by adding fluorides, fluorine complex salts, oxides, etc. of these elements as raw materials. It is possible to improve the solarization of glass and to diversify its optical properties.
尚、原料中の不純物遷移金属元素、特にＣｒ、 Ｍｎ、
Ｆｅ、 Ｃｏ、 Ｎｉ及びＣｕ元素の重量含有率を、合
計で３ｐｐ−以下としたガラスは、紫外域で高い光線透
過率を得ることができ、２５０ｎｍでの光線透過率は、
８０％以上に及ぶ。In addition, impurity transition metal elements in the raw materials, especially Cr, Mn,
Glass with a total weight content of Fe, Co, Ni, and Cu elements of 3 pp- or less can obtain high light transmittance in the ultraviolet region, and the light transmittance at 250 nm is
It accounts for over 80%.
以下に、本発明における光学ガラスの実施例の組成（モ
ル％表示）、屈折率ｎ４、アツベ数ν４及び比重Ｓｇ、
を、それぞれ第１表に示す。第１表において、上段は弗
化物としての表記、下段は上段の組成に対応する原料と
しての表記であり、ともにモル％で示しである。Below, the composition (in mol%), refractive index n4, Atsube number ν4, and specific gravity Sg of the optical glass in the present invention are shown below.
are shown in Table 1. In Table 1, the upper row shows the description as a fluoride, and the lower row shows the description as a raw material corresponding to the composition in the upper row, both of which are expressed in mol%.
また、第２表では、市販の弗燐酸塩光学ガラスの比重と
、それとばば等しい光学恒数値を持つ本発明のガラスの
比重とを比較した。Table 2 also compares the specific gravity of a commercially available fluorophosphate optical glass and the specific gravity of the glass of the present invention, which has exactly the same optical constant value.
本発明の第１表の実施例に掲げたガラスは、下段に記載
の原料を所望の割合に秤取、混合して、９００〜１１０
０℃の電気炉中、白金坩堝に入れて溶融、清澄、撹拌、
均質化してから鋳込み、徐冷して製造することができる
。The glasses listed in the examples in Table 1 of the present invention are made by weighing and mixing the raw materials listed in the lower column in the desired proportions,
Melt, clarify, stir, and melt in a platinum crucible in an electric furnace at 0°C.
It can be manufactured by homogenizing, casting, and slow cooling.
第 １ 表
第 １ 表（続き）
第
表
（続き）
第
■
表
（続き）
第
表
（続き）
第
表
（続き）
第
表
（続き）
第
表
（続き）
第
表
（続き）
第
表
（比重の比較）
第
表
（続き）
第
表
（続き）
〔発明の効果〕
以上の通り、本発明によれば、比重が３．６以下と軽く
（同一光学恒数のガラスで比較すると必ず軽い）、屈
折率ｎ４が１．４２〜１．５０、アツベ数ν４が８０〜
９７の範囲にあり、異常部分分散性を有し、加工性に優
れ、大口径レンズを得る際にも失透に対して安定で、工
業的規模での生産が可能な、軽量弗燐酸塩光学ガラスが
得られる。Table 1 Table 1 (continued) Table (continued) ■ Table (continued) Table (continued) Table (continued) Table (continued) Table (continued) Table (continued) Table (continued) Comparison) Table (Continued) Table (Continued) [Effects of the Invention] As described above, according to the present invention, the specific gravity is light at 3.6 or less (it is always light when comparing glasses with the same optical constant), and the refraction is Rate n4 is 1.42 to 1.50, Atsbe number ν4 is 80 to
97 range, has anomalous partial dispersion, has excellent processability, is stable against devitrification even when obtaining large diameter lenses, and can be produced on an industrial scale. glass is obtained.
Claims (1)
＾２＾−とを含み、ガラス中の陽イオンを弗化物として
表記した場合、モル％で、 ＰＦ＿５５．０〜３０．０％ ＡｌＦ＿３１９．０〜４０．０％ ＣａＦ＿２２８．０〜５６．０％ ＭｇＦ＿２０〜２０．０％ ＳｒＦ＿２０〜９．０％ ＢａＦ＿２０〜１８．０％ ＺｎＦ＿２０〜１０．０％ ＮａＦ０〜４．０％ ＸＦ０〜４．０％ ＹＦ＿３０〜１３．０％ ＬａＦ＿３０〜７．０％ の組成範囲を有し、ガラス中におけるＦ＾−／Ｏ＾２＾
−（酸素イオン数に対する弗素イオン数の比）が、１．
４〜１３．０の範囲にあり、比重が３．６以下であるこ
とを特徴とする軽量弗燐酸塩光学ガラス。 ２ 特許請求の範囲第１項記載の弗燐酸塩光学ガラスに
おいて、特にＰＦ＿５、ＮａＦ及びＫＦの組成範囲が、
モル％で、 ＰＦ＿５８．０〜３０．０％ ＮａＦ０ ＫＦ０ であり、ガラス中におけるＦ＾−／Ｏ＾２＾−（酸素イ
オン数に対する弗素イオン数の比）が、１．４〜９．０
の範囲にあることを特徴とするガラス。 ３ 特許請求の範囲第２項記載の弗燐酸塩光学ガラスに
おいて、特にＭｇＦ＿２及びＢａＦ＿２の組成範囲が、
モル％で、 ＭｇＦ＿２０．５〜２０．０％ ＢａＦ＿２０〜１３．０％ であることを特徴とするガラス。 ４ 特許請求の範囲第３項記載の弗燐酸塩光学ガラスに
おいて、特にＡｌＦ＿３及びＣａＦ＿２の組成範囲が、
モル％で、 ＡｌＦ＿３２０．０〜３６．０％ ＣａＦ＿２２８．０〜４８．０％ であることを特徴とするガラス。[Claims] 1. Fluorine ion F^- and oxygen ion O as anions
＾2＾-, and when the cation in the glass is expressed as fluoride, in mol%, PF_55.0-30.0% AlF_319.0-40.0% CaF_228.0-56.0% MgF_20 ~20.0% SrF_20-9.0% BaF_20-18.0% ZnF_20-10.0% NaF0-4.0% XF0-4.0% YF_30-13.0% LaF_30-7.0% Composition range and F^-/O^2^ in the glass
- (ratio of the number of fluorine ions to the number of oxygen ions) is 1.
A lightweight fluorophosphate optical glass characterized by having a specific gravity in the range of 4 to 13.0 and a specific gravity of 3.6 or less. 2 In the fluorophosphate optical glass according to claim 1, in particular, the composition range of PF_5, NaF and KF is
In mol%, PF_58.0-30.0% NaF0 KF0, and F^-/O^2^- (ratio of the number of fluorine ions to the number of oxygen ions) in the glass is 1.4-9.0.
Glass characterized by being in the range of. 3 In the fluorophosphate optical glass according to claim 2, in particular, the composition range of MgF_2 and BaF_2 is
A glass characterized in that, in terms of mol%, MgF_20.5-20.0% BaF_20-13.0%. 4 In the fluorophosphate optical glass according to claim 3, in particular, the composition range of AlF_3 and CaF_2 is
A glass characterized in that, in terms of mol%, AlF_320.0-36.0% CaF_228.0-48.0%.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2117386A JP2727735B2 (en) | 1990-05-07 | 1990-05-07 | Lightweight fluorophosphate optical glass |
| DE4114790A DE4114790C2 (en) | 1990-05-07 | 1991-05-06 | Lightweight optical fluorophosphate glass |
| US07/924,579 US5246891A (en) | 1990-05-07 | 1992-08-05 | Light-weight optical glass of fluoro-phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2117386A JP2727735B2 (en) | 1990-05-07 | 1990-05-07 | Lightweight fluorophosphate optical glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0416526A true JPH0416526A (en) | 1992-01-21 |
| JP2727735B2 JP2727735B2 (en) | 1998-03-18 |
Family
ID=14710367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2117386A Expired - Lifetime JP2727735B2 (en) | 1990-05-07 | 1990-05-07 | Lightweight fluorophosphate optical glass |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2727735B2 (en) |
| DE (1) | DE4114790C2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0948633A (en) * | 1995-08-02 | 1997-02-18 | Nikon Corp | Optical glass for polarizing optical system and polarizing light beam splitter using the same |
| JP2009203114A (en) * | 2008-02-28 | 2009-09-10 | Hoya Corp | Fluorophosphate glass, glass material for press molding, optical element blank, optical elements, those producing methods, and producing method of glass molded article |
| JP2012153602A (en) * | 2007-03-06 | 2012-08-16 | Hoya Corp | Optical glass, preform for press forming, optical element, and method of manufacturing the same |
| JP2019085326A (en) * | 2017-11-02 | 2019-06-06 | Hoya株式会社 | Optical glass and optical element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5571643A (en) * | 1978-11-21 | 1980-05-29 | Nippon Kogaku Kk <Nikon> | Fluorophosphate optical glass |
| JPS6081042A (en) * | 1983-10-08 | 1985-05-09 | Ohara Inc | Optical fluorophosphate glass |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1405717A (en) * | 1973-04-02 | 1975-09-10 | Tallin Stekolny Z Tarbeklaas | Optical glass |
| JPS5434768B2 (en) * | 1973-04-03 | 1979-10-29 | ||
| JPS55144448A (en) * | 1979-04-24 | 1980-11-11 | Nippon Kogaku Kk <Nikon> | Fluorophosphate optical glass |
| DE3634676A1 (en) * | 1985-10-19 | 1987-04-23 | Leitz Ernst Gmbh | OPTICAL FLUORPHOSPHATE GLASSES WITH POSITIVE ANOMAL PARTIAL DISPERSION AND IMPROVED PHYSICO-CHEMICAL PROPERTIES AND METHOD FOR THE PRODUCTION THEREOF |
-
1990
- 1990-05-07 JP JP2117386A patent/JP2727735B2/en not_active Expired - Lifetime
-
1991
- 1991-05-06 DE DE4114790A patent/DE4114790C2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5571643A (en) * | 1978-11-21 | 1980-05-29 | Nippon Kogaku Kk <Nikon> | Fluorophosphate optical glass |
| JPS6081042A (en) * | 1983-10-08 | 1985-05-09 | Ohara Inc | Optical fluorophosphate glass |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0948633A (en) * | 1995-08-02 | 1997-02-18 | Nikon Corp | Optical glass for polarizing optical system and polarizing light beam splitter using the same |
| JP2012153602A (en) * | 2007-03-06 | 2012-08-16 | Hoya Corp | Optical glass, preform for press forming, optical element, and method of manufacturing the same |
| JP2009203114A (en) * | 2008-02-28 | 2009-09-10 | Hoya Corp | Fluorophosphate glass, glass material for press molding, optical element blank, optical elements, those producing methods, and producing method of glass molded article |
| JP2019085326A (en) * | 2017-11-02 | 2019-06-06 | Hoya株式会社 | Optical glass and optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4114790A1 (en) | 1991-11-14 |
| DE4114790C2 (en) | 2003-04-17 |
| JP2727735B2 (en) | 1998-03-18 |
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