JPH0383835A - Fluorophosphate glass - Google Patents
Fluorophosphate glassInfo
- Publication number
- JPH0383835A JPH0383835A JP22131889A JP22131889A JPH0383835A JP H0383835 A JPH0383835 A JP H0383835A JP 22131889 A JP22131889 A JP 22131889A JP 22131889 A JP22131889 A JP 22131889A JP H0383835 A JPH0383835 A JP H0383835A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- metal
- fluoride
- total amount
- cuo
- 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
- 239000005303 fluorophosphate glass Substances 0.000 title claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract 3
- 229910052788 barium Inorganic materials 0.000 claims abstract 2
- 239000006121 base glass Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 30
- 238000002834 transmittance Methods 0.000 abstract description 14
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- 239000005365 phosphate glass Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 Cu2+ ions Chemical class 0.000 description 3
- 229910001632 barium fluoride Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 3
- 229910005693 GdF3 Inorganic materials 0.000 description 2
- 229910002319 LaF3 Inorganic materials 0.000 description 2
- 101000929049 Xenopus tropicalis Derriere protein Proteins 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 229910004546 TaF5 Inorganic materials 0.000 description 1
- 229910009520 YbF3 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 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
Landscapes
- 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
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、弗燐酸塩ガラスに関し、例えばカラーＶＴＲ
カメラの色補正に用いて好適なフィルターガラスに関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to fluorophosphate glass, for example, color VTR glass.
The present invention relates to a filter glass suitable for use in color correction of cameras.
［従来の技術］
一般に、カラーＶＴＲカメラに使用されている撮像管の
光の分光感度は、可視域から近赤外域９５０ｎｍまでの
びているため、この近赤外域をフィルターによりカット
し分光感度を人間の視感度に近似させてやらなければ、
画像が赤味を帯び、良好な色再現を得ることができない
。また一方で、フィルターの紫外域側の吸収が可視域ま
で及ぶと、今度は画像が暗くなってしまうことになる。[Prior Art] Generally, the spectral sensitivity of the light from the image pickup tube used in a color VTR camera extends from the visible region to the near-infrared region of 950 nm, so this near-infrared region is cut by a filter to reduce the spectral sensitivity to that of humans. Unless it is approximated to visual sensitivity,
The image becomes reddish and good color reproduction cannot be obtained. On the other hand, if the filter's absorption in the ultraviolet region extends to the visible region, the image will become darker.
従ってこの種のフィルターには、４００〜５２０ｎｍの
光の透過率が可能な限り高く、５５０〜９５０ｎｍの光
を可能な限り多く吸収する特性が必要とされる。従来よ
りこの種の近赤外線吸収フィルターとしては、燐酸塩ガ
ラスにＣｕＯを添加したガラスが用いられる。Therefore, this type of filter is required to have as high a transmittance as possible for light in the wavelength range of 400 to 520 nm and to absorb as much light as possible in the wavelength range of 550 to 950 nm. Conventionally, as this type of near-infrared absorbing filter, glass obtained by adding CuO to phosphate glass has been used.
［発明が解決しようとする手段］
しかしながら、燐酸塩ガラスは、元々耐候性が悪いこと
から、それを実用に耐え得るまで向上させるには、例え
ば特開昭６２−１２８９４３号公報に開示されているよ
うに比較的多量のＡｌ２Ｏ３の添加を必要とする。その
結果、溶融温度が上昇し、その温度が高いほど、銅イオ
ンは還元されやすい傾向にあるので、近赤外域に吸収を
もつガラス成分中の銅の２価のＣｕ２＋イオンが還元さ
れ、紫外域に吸収をもっ１価のＣｕ＋イオンに変化し、
可視域の透過率が低くなり、赤外域の透過率が高くなる
という特性劣化の傾向が生じていた。反対に透過率特性
を向上させようとすると、ガラス成分中の２価のＣｕ２
″″イオンが還元されて１価のＣｕ＋イオンにならない
ようにアルカリ金属酸化物の添加等で溶融温度を下げる
ことになるが、これは同時にガラスそのものの耐候性を
さらに劣化させることとなる。したがって燐酸塩ガラス
でこの種の近赤外域吸収フィルターを製作する場合には
、相反する関係の透過率特性と耐候性との妥協点をみつ
けて実用に提供してきたのが実状である。[Means to be Solved by the Invention] However, since phosphate glass originally has poor weather resistance, in order to improve it to a point where it can withstand practical use, there is a method disclosed, for example, in JP-A-62-128943. Therefore, it is necessary to add a relatively large amount of Al2O3. As a result, the melting temperature rises, and the higher the temperature, the more easily copper ions are reduced, so the divalent Cu2+ ions of copper in the glass component that absorbs in the near-infrared region are reduced, and The absorption changes to monovalent Cu+ ions,
There was a tendency for characteristics to deteriorate, with transmittance in the visible region becoming lower and transmittance in the infrared region increasing. On the other hand, when trying to improve the transmittance characteristics, divalent Cu2 in the glass component
In order to prevent the ``'' ions from being reduced to monovalent Cu+ ions, the melting temperature is lowered by adding an alkali metal oxide, but at the same time, this further deteriorates the weather resistance of the glass itself. Therefore, when producing this type of near-infrared absorption filter using phosphate glass, the actual situation is to find a compromise between the contradictory relationship between transmittance characteristics and weather resistance and to provide it for practical use.
本発明は、前述した従来の問題点に鑑みてなされたもの
であり、その目的は、カラーＶＴＲフィルターに要求さ
れる近赤外域吸収フィルターとしての透過率特性を十分
に満足し、かつ実用に十分に耐えうる耐候性を有する弗
燐酸塩ガラスを提供することにある。The present invention has been made in view of the above-mentioned conventional problems, and its purpose is to fully satisfy the transmittance characteristics as a near-infrared absorption filter required for color VTR filters, and to provide a filter that is sufficient for practical use. An object of the present invention is to provide a fluorophosphate glass having weather resistance that can withstand the weather conditions.
［課題を解決するための手段］
本発明は上記の目的を達成するためになされたものであ
り、本発明の弗燐酸塩ガラスは、重量％で０．５〜３８
．５％のＰ＝ ｏ５．１〜１５％のＡ１Ｆ３、０〜９．
９％のＫＦ２ （Ｒは原子価が２価の金属であるＢａ
、 Ｓｒ、 Ｃａ、 Ｍｇ、 ＺｎおよびＰｂか
ら選ばれる少なくとも１種である）、０〜２３％のＲ’
Ｆ （Ｒ’は原子価が１価の金属であるＬｉ、Ｎａお
よびＫから選ばれる少なくとも１種である）、１〜３３
％のＫＦ２およびＲ’ Ｆの合量、Ｏ〜６８．５％のＲ
’ Ｆｍ （Ｒ’は原子価が３〜５価の金属であるＬａ
、 Ｙ、 Ｇｄ。[Means for Solving the Problems] The present invention has been made to achieve the above objects, and the fluorophosphate glass of the present invention has a content of 0.5 to 38% by weight.
．． 5% P=o5.1-15% A1F3, 0-9.
9% KF2 (R is Ba, a divalent metal)
, Sr, Ca, Mg, Zn and Pb), 0 to 23% R'
F (R' is at least one selected from monovalent metals Li, Na, and K), 1 to 33
Total amount of KF2 and R'F in %, R of O~68.5%
' Fm (R' is La, which is a trivalent to pentavalent metal)
, Y, Gd.
Ｓｉ、Ｂ、Ｚｒ、ＴａおよびＹｂから選ばれる少なくと
も１種であり、ｍはＲ′の原子価に相当する数である）
を含有し、さらに金属酸化物を式％式％
（式中Ｘは金属酸化物（Ｐｇ ０５を除く）の合量であ
り、ｙは全弗化物の合量である）
を満足するように含有する基礎ガラス１００重量部と、
０．２〜１５重量部のＣｕＯとを含むことを特徴とする
。At least one selected from Si, B, Zr, Ta and Yb, m is a number corresponding to the valence of R')
and further contains metal oxides to satisfy the formula % (in the formula, X is the total amount of metal oxides (excluding Pg 05) and y is the total amount of all fluorides). 100 parts by weight of base glass,
It is characterized by containing 0.2 to 15 parts by weight of CuO.
本発明の弗燐酸塩ガラスは、耐候性悪化の原因となるｐ
２ ｏ５の量を比較的少量に抑えたものである。すなわ
ち、ｐｔ ｏ５の上限は耐候性の低下を防止するために
３８．５％とされる。一方、ｐ２ ｏ５を０．５％未満
とするε、ガラス化が困難となるので、Ｐ２Ｏ５の下限
は０．５％とされる。また、ＡｌＦ３は耐候性を向上さ
せるのに有効な成分てあり、１％未満ではその効果が得
られず、１５％を越えると、ガラスの溶融性が低下する
。したがってＡｌＦ３は１〜１５％の範囲に限定される
。また、２偏成分ＲＦ！および１偏成分Ｒ’ Ｆはガラ
スの溶融性を向上させるのに有効な成分であり、その合
量が１％未満ではガラス化しにくく、３３％を越えると
ガラスが軟らかくなりすぎて、量産時の底形に困難をき
たし、かつ耐候性を低下させる等の問題を発生させる。The fluorophosphate glass of the present invention is free from p, which causes deterioration in weather resistance.
The amount of 2 o5 is kept to a relatively small amount. That is, the upper limit of pt o5 is set to 38.5% in order to prevent a decrease in weather resistance. On the other hand, when p2o5 is less than 0.5%, vitrification becomes difficult, so the lower limit of P2O5 is set to 0.5%. Furthermore, AlF3 is an effective component for improving weather resistance, and if it is less than 1%, the effect cannot be obtained, and if it exceeds 15%, the meltability of the glass is reduced. Therefore, AlF3 is limited to a range of 1 to 15%. Also, 2 polarized component RF! The one-part component R'F is an effective component for improving the meltability of glass. If the total amount is less than 1%, it will be difficult to vitrify, and if it exceeds 33%, the glass will become too soft, making it difficult to use during mass production. This causes problems such as making the bottom shape difficult and reducing weather resistance.
したがってＫＦ２およびＲ’ Ｆの合量は１〜３３％の
範囲に限定される。ただし、ＫＦ２は９．９％を越える
とガラスの粘性が下がり過ぎるので０〜９．９％の範囲
に、Ｒ’ Ｆは２３％を越えると耐候性が低下するので
０〜２３％の範囲に限定される。さらに、ＫＦ２のうち
、ＢａＦ２ 、Ｓ ｒＦ２ 。Therefore, the total amount of KF2 and R'F is limited to a range of 1 to 33%. However, if KF2 exceeds 9.9%, the viscosity of the glass will drop too much, so keep it in the range of 0 to 9.9%, and for R'F, if it exceeds 23%, the weather resistance will decrease, so keep it in the range of 0 to 23%. Limited. Furthermore, among KF2, BaF2 and S rF2.
ＰｂＦ２はそれぞれ９．９％を越えると、ガラスの粘性
が下がりすぎるので０〜９．９％の範囲とし、ＣａＦ２
、ＭｇＦ２ 、ＺｎＦ２はそれぞれ９゜０％を越える
と、ガラスの粘性が下がりすぎるのでＯ〜９．０％の範
囲とするのが好ましい。If PbF2 exceeds 9.9%, the viscosity of the glass decreases too much, so it should be in the range of 0 to 9.9%, and CaF2
, MgF2, and ZnF2, if each exceeds 9.0%, the viscosity of the glass decreases too much, so it is preferable that the content is in the range of O to 9.0%.
またＲ’ ＦであるＬｉＦ、ＮａＦ、ＫＦはそれぞれ
２０％を越えると、耐候性を低下させるので、０〜２０
％の範囲とするのが好ましい。さらに他の弗化物として
高原子価成分Ｒ’ Ｆｍを添加すると、透過率特性に悪
影響を与えることなく、耐磨耗性を改善することができ
るが、この高分子偏成分はその合量が６８．５％を越え
ると、ガラスの耐失透性が悪化する。したがってこの高
原子価成分の合量は０〜６８．５％の範囲に限定される
。In addition, if the R'Fs LiF, NaF, and KF each exceed 20%, the weather resistance will decrease, so 0 to 20%
It is preferable to set it as the range of %. Furthermore, if a high valence component R' Fm is added as another fluoride, the abrasion resistance can be improved without adversely affecting the transmittance characteristics, but the total amount of this high molecular component is 68 If it exceeds .5%, the devitrification resistance of the glass will deteriorate. Therefore, the total amount of these high valence components is limited to a range of 0 to 68.5%.
ただし、高原子価成分Ｒ’ Ｆｍ中のＬａＦ３゜ＹＦ３
．ＧｄＦ３．ＹｂＦ３がそれぞれ６０％を越えると失透
しやすくなるので、０〜６０％の範囲とするのが好まし
く、またＳｉＦ４、ＢＦ３゜ＺｒＦ４．ＴａＦ５がそれ
ぞれ５０％を越えると失透しやすくなるので、０〜５０
％の範囲とするのが好ましい。However, LaF3゜YF3 in the high valence component R' Fm
．． GdF3. If YbF3 exceeds 60% each, devitrification tends to occur, so it is preferably in the range of 0 to 60%, and SiF4, BF3゜ZrF4. If TaF5 exceeds 50% each, devitrification tends to occur, so 0 to 50%
It is preferable to set it as the range of %.
本発明の弗燐酸塩ガラスは、さらに金属酸化物を式
％式％
（式中Ｘは金属酸化物（Ｐ２０５を除く）の合量であり
、ｙは全弗化物の合量である）
を満足するように含有する。The fluorophosphate glass of the present invention further contains metal oxides that satisfy the following formula % (where X is the total amount of metal oxides (excluding P205) and y is the total amount of all fluorides). Contain so as to.
ｙ／ （ｘ＋ｙ）が０．０５未満または０．８０を越え
ると、目的とする優れた耐候性および透過率特性が得ら
れない。When y/(x+y) is less than 0.05 or more than 0.80, the desired excellent weather resistance and transmittance characteristics cannot be obtained.
金属酸化物の金属種は、Ａ１および上述のＲ９Ｒ’ 、
Ｒ’として定義されたものが用いられる。The metal species of the metal oxide are A1 and the above-mentioned R9R',
The one defined as R' is used.
なお金属酸化物のうち、Ａｌ２Ｏ３は１０％を越えると
溶融性が悪くなるので、０〜１０％の範囲とするのが好
ましい。またＬａ２Ｏ３゜Ｇｄ２０ｓ、Ｙｇ ０３およ
びＹｂ２ ｏ３は６０％を越えると溶融性が悪くなるの
で、０〜６０％の範囲とするのが好ましい。また５ｉ０
２゜Ｂ２０３．ＺｒＯ２およびＴａ２０５は５０％を越
えると失透しやす（なるので、０〜５０％の範囲とする
のが好ましい。またＭｇＯ，Ｃａｂ。Note that among the metal oxides, if Al2O3 exceeds 10%, the meltability deteriorates, so it is preferably in the range of 0 to 10%. Furthermore, if La2O3°Gd20s, Yg03, and Yb2o3 exceed 60%, the meltability deteriorates, so it is preferable that the content is in the range of 0 to 60%. Also 5i0
2°B203. If ZrO2 and Ta205 exceed 50%, they tend to devitrify, so the range is preferably from 0 to 50%.Also, MgO, Cab.
ＳｒＯおよびＢａＯは６０％を越えると失透しやすくな
るので、０〜６０％の範囲とするのが好ましい。またＬ
ｉＯ２、Ｎａｇ Ｏ，に２０は２０％を越えると耐候性
および耐失透性が悪くなるので、０〜２０％の範囲とす
るのが好ましい。If SrO and BaO exceed 60%, devitrification tends to occur, so it is preferable that the content is in the range of 0 to 60%. Also L
When iO2, Nag O, and 20 exceed 20%, weather resistance and devitrification resistance deteriorate, so it is preferably in the range of 0 to 20%.
本発明の弗燐酸塩ガラスは、上述のｐ！ ｏ５ 。The fluorophosphate glass of the present invention has the above p! o5.
Ａ１Ｆ３、ＢＦ２ 、Ｒ’ Ｆ、Ｒ’ Ｆｍおよび金属
酸化物を含有する基礎ガラス１００重量部に対して０．
２〜１５重量部のＣｕＯを含むものである。0.0 parts by weight per 100 parts by weight of the basic glass containing A1F3, BF2, R'F, R'Fm and metal oxides.
It contains 2 to 15 parts by weight of CuO.
ＣｕＯは近赤外域吸収のための必須成分であり、ＣｕＯ
の量を０．２〜１５重量部に限定したのは、０゜２重量
部未満ではその吸収が不十分となり、一方１５重量部を
越えると、ガラスの耐失透性が悪化するからである。CuO is an essential component for near-infrared absorption, and CuO
The reason why the amount is limited to 0.2 to 15 parts by weight is that if it is less than 0.2 parts by weight, its absorption will be insufficient, while if it exceeds 15 parts by weight, the devitrification resistance of the glass will deteriorate. .
本発明の弗燐酸塩ガラスの特に好ましい組成を示すと以
下の通りである。A particularly preferred composition of the fluorophosphate glass of the present invention is as follows.
基礎ガラス Ｐ２Ｏ５２〜３７％
ＡｌＦ３ １〜１３％
ＢＦ２ ０〜９．９％
Ｒ’ＦＯ〜２０％
ＲＦ２＋Ｒ’Ｆ１〜３３％
Ｒ″ＦｍＯ〜６５％
ｙ／（ｘ＋ｙ） ０． １０〜０．７５ＣｕＯＯ，２
〜１３重量部（基礎ガラス１００重量部に対して）
［実施例］
以下実施例により本発明を更に説明する。Basic glass P2O52~37% AlF3 1~13% BF2 0~9.9% R'FO~20% RF2+R'F1~33% R″FmO~65% y/(x+y) 0.10~0.75CuOO,2
~13 parts by weight (based on 100 parts by weight of the base glass) [Examples] The present invention will be further explained below with reference to Examples.
実施例１〜１１
原料として正燐酸水溶液、炭酸バリウム、弗化アルミニ
ウム、弗化ランタン、弗化イツトリウム、弗化ガドリニ
ウム、弗化バリウム、酸化バリウム、酸化第２銅を所定
量混合しくなお原料として燐酸アルミニウム、燐酸バリ
ウム等の複合塩の使用を妨げるものではない）、白金製
るつぼで、蓋をして８００〜９００℃で溶解し、撹拌し
て脱泡、均質化を行った後、予熱した金型に鋳込み、徐
冷することによって、重量％で２１．４％のｐ２ｏ５゜
１．５％のＡ１Ｆ３、９．５％のＢａＦ２゜７．５％の
ＬａＦ３，１４．７％のＹＦ３ 。Examples 1 to 11 Mix predetermined amounts of orthophosphoric acid aqueous solution, barium carbonate, aluminum fluoride, lanthanum fluoride, yttrium fluoride, gadolinium fluoride, barium fluoride, barium oxide, and cupric oxide as raw materials, and then use phosphoric acid as raw materials. (This does not preclude the use of complex salts such as aluminum and barium phosphate), melt in a platinum crucible at 800 to 900°C with a lid, stir to defoam and homogenize, and then preheat the gold. By casting into a mold and slowly cooling, the resulting mixture was 21.4% p2o5, 1.5% A1F3, 9.5% BaF2, 7.5% LaF3, and 14.7% YF3 by weight.
１２．８％のＧｄＦ３および３２．６％のＢａＯを含有
し、ｙ／ （ｘ＋ｙ）が０．５９である基礎ガラス１０
０重量部に１．４５重量部のＣｕＯを含有する、実施例
１の弗燐酸塩ガラスを得た。Base glass 10 containing 12.8% GdF3 and 32.6% BaO with y/(x+y) of 0.59
A fluorophosphate glass of Example 1 containing 1.45 parts by weight of CuO in 0 parts by weight was obtained.
以下同様にして実施例２〜１１の弗燐酸塩ガラスを得た
。これら実施例１〜１１の弗燐酸塩ガラスの組成は表−
１にまとめて示した。Thereafter, fluorophosphate glasses of Examples 2 to 11 were obtained in the same manner. The compositions of the fluorophosphate glasses of Examples 1 to 11 are shown in Table-
They are summarized in 1.
次に、このようにして得られた実施例１〜１１の弗燐酸
塩ガラスの耐候性を、研摩したガラスを約６５℃、９０
％相対湿度の恒温恒湿条件下に保持し、一定時間毎にそ
の表面状態を観察し、ガラス表面に変質が見られるまで
の時間を求めることで評価した。その結果は表−１に示
すように、実施例１の弗燐酸塩ガラスは、ガラス表面に
変質が見られるまでの時間が９８０時間で耐候性に極め
て優れていた。また実施例２〜１１の弗燐酸塩ガラスで
もガラス表面に変質が見られるまでの時間がいずれも９
５０時間以上であり（実施例５，７゜９の弗燐酸塩ガラ
スでは１０１０時間である）、耐候性に極めて優れてい
た。Next, the weather resistance of the fluorophosphate glasses of Examples 1 to 11 obtained in this way was evaluated by polishing the polished glasses at about 65°C and 90°C.
% relative humidity, the surface condition was observed at regular intervals, and the evaluation was made by determining the time until deterioration was observed on the glass surface. As the results are shown in Table 1, the fluorophosphate glass of Example 1 had extremely excellent weather resistance, with a time period of 980 hours until deterioration was observed on the glass surface. Furthermore, for the fluorophosphate glasses of Examples 2 to 11, the time until deterioration was observed on the glass surface was 9.
It was 50 hours or more (1010 hours for the fluorophosphate glass of Examples 5 and 7°9), and had extremely excellent weather resistance.
これに対し、特開昭６２−１２８９４３号公報に記載さ
れた燐酸塩ガラスに相当する比較例１゜２の燐酸塩ガラ
ス（７０％以上のｐ２ ｏ５と比較的多量のＡｌ２Ｏ３
を含有する）は、表−１に示すように、ガラス表面に変
質が見られる時間がそれぞれ２４０時間、２１６時間で
、約８００時間を経た時点では完全に白（変質し、ガラ
スの透明度を失うに至った。In contrast, the phosphate glass of Comparative Example 1゜2, which corresponds to the phosphate glass described in JP-A No. 62-128943 (with a p2 o5 of 70% or more and a relatively large amount of Al2O3
As shown in Table 1, it takes 240 hours and 216 hours for the glass surface to show deterioration, and after about 800 hours it becomes completely white (deterioration occurs and the glass loses its transparency). reached.
以上のことから、本発明の弗燐酸塩ガラスは従来の燐酸
塩ガラスよりも耐候性に著るしく優れていることが明ら
かとなった。From the above, it has become clear that the fluorophosphate glass of the present invention has significantly better weather resistance than conventional phosphate glasses.
次に実施例１． ３． １１および比較例１．２のガラ
スの分光透過率曲線を第１図に示す。なお測定に供した
ガラスの肉厚は１． ６ｍｍである。同図から明らかな
ように実施例１． ３． １１のガラスは、弗化物を含
まない燐酸塩ベースの比較例１゜２のガラスに比べて波
長３６０〜５００ｎｍにおける透過率が高（、それより
長波長側の５５０〜９５０ｎｍの光を十分に吸収するカ
ラーＶＴＲカメラ用フィルターとして優れた分光透過率
を有していることが明らかとなった。Next, Example 1. 3. The spectral transmittance curves of the glasses of Comparative Example 1.1 and Comparative Example 1.2 are shown in FIG. The wall thickness of the glass used for measurement was 1. It is 6mm. As is clear from the figure, Example 1. 3. Glass No. 11 has a higher transmittance in the wavelength range of 360 to 500 nm than the fluoride-free phosphate-based glass of Comparative Example 1. It has become clear that the filter has excellent spectral transmittance as a filter for color VTR cameras.
（以下余白）
［発明の効果］
以上説明したように本発明によれば、従来得られなかっ
た極めて優れた耐候性を有すると同時に分光透過率特性
も一層向上した弗燐酸塩ガラスが提供された。(The following is a blank space) [Effects of the Invention] As explained above, according to the present invention, a fluorophosphate glass is provided which has extremely excellent weather resistance that has not been previously available and at the same time has further improved spectral transmittance characteristics. .
第１図は本発明の弗燐酸塩ガラスと従来の燐酸塩ガラス
の分光透過率の差異を示す特性図である。FIG. 1 is a characteristic diagram showing the difference in spectral transmittance between the fluorophosphate glass of the present invention and the conventional phosphate glass.
Claims (1)
〜１５％のＡ１Ｆ＿３、０〜９．９％のＲＦ＿２（Ｒは
原子価が２価の金属であるＢａ、Ｓｒ、Ｃａ、Ｍｇ、Ｚ
ｎおよびＰｂから選ばれる少なくとも１種である）、０
〜２３％のＲ’Ｆ （Ｒ’は原子価が１価の金属であるＬｉ、ＮａおよびＫ
から選ばれる少なくとも１種である）、１〜３３％のＲ
Ｆ＿２およびＲ’Ｆの合量、０〜６８．５％のＲ″Ｆｍ
（Ｒ″は原子価が３〜５価の金属であるＬａ、Ｙ、Ｇｄ
、Ｓｉ、Ｂ、Ｚｒ、ＴａおよびＹｂから選ばれる少なく
とも１種であり、ｍはＲ″の原子価に相当する数である
）を含有し、さらに金属酸化物を式 ｙ／（ｘ＋ｙ）＝０．０５〜０．８０ （式中ｘは金属酸化物（Ｐ＿２Ｏ＿５を除く）の合量で
あり、ｙは全弗化物の合量である） を満足するように含有する基礎ガラス１００重量部と、
０．２〜１５重量部のＣｕＯとを含むことを特徴とする
弗燐酸塩ガラス。(1) 0.5-38.5% P_2O_5,1 by weight%
~15% A1F_3, 0~9.9% RF_2 (R is a divalent metal Ba, Sr, Ca, Mg, Z
at least one selected from n and Pb), 0
~23% R'F (R' is monovalent metals Li, Na, and K
), 1 to 33% R
Total amount of F_2 and R'F, R″Fm of 0 to 68.5%
(R″ is a trivalent to pentavalent metal such as La, Y, or Gd.
, Si, B, Zr, Ta, and Yb, and m is a number corresponding to the valence of R''), and the metal oxide has the formula y/(x+y)=0 .05 to 0.80 (in the formula, x is the total amount of metal oxides (excluding P_2O_5) and y is the total amount of all fluorides) 100 parts by weight of a base glass containing the following:
A fluorophosphate glass comprising 0.2 to 15 parts by weight of CuO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22131889A JPH0774083B2 (en) | 1989-08-28 | 1989-08-28 | Fluorophosphate glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22131889A JPH0774083B2 (en) | 1989-08-28 | 1989-08-28 | Fluorophosphate glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0383835A true JPH0383835A (en) | 1991-04-09 |
| JPH0774083B2 JPH0774083B2 (en) | 1995-08-09 |
Family
ID=16764925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22131889A Expired - Fee Related JPH0774083B2 (en) | 1989-08-28 | 1989-08-28 | Fluorophosphate glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774083B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007101585A (en) * | 2005-09-30 | 2007-04-19 | Hoya Corp | Lens and manufacturing method thereof |
| EP1466875A3 (en) * | 2003-04-09 | 2007-05-30 | Hoya Corporation | Glass for window of semiconductor package, glass window for semiconductor package, process for production of glass window, and semiconductor package |
| JP2013053058A (en) * | 2011-08-11 | 2013-03-21 | Hoya Corp | Fluorophosphate glass, method of manufacturing the same, and near infrared light absorbing filter |
| JP2013151410A (en) * | 2011-12-28 | 2013-08-08 | Ohara Inc | Optical glass, optical element and preform |
| JP2013151411A (en) * | 2011-12-28 | 2013-08-08 | Ohara Inc | Optical glass, optical element and preform |
| JP2015205785A (en) * | 2014-04-17 | 2015-11-19 | 株式会社住田光学ガラス | Optical glass, preform for forming accurate press and optical element |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923950B (en) * | 2011-08-11 | 2016-08-17 | Hoya株式会社 | Fluophosphate glass and manufacture method thereof and near-infrared absorption filter |
| CN103708727B (en) * | 2012-09-29 | 2016-08-03 | 成都光明光电股份有限公司 | Fluorophosphate optical glass |
-
1989
- 1989-08-28 JP JP22131889A patent/JPH0774083B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1466875A3 (en) * | 2003-04-09 | 2007-05-30 | Hoya Corporation | Glass for window of semiconductor package, glass window for semiconductor package, process for production of glass window, and semiconductor package |
| JP2007101585A (en) * | 2005-09-30 | 2007-04-19 | Hoya Corp | Lens and manufacturing method thereof |
| JP2013053058A (en) * | 2011-08-11 | 2013-03-21 | Hoya Corp | Fluorophosphate glass, method of manufacturing the same, and near infrared light absorbing filter |
| JP2013151410A (en) * | 2011-12-28 | 2013-08-08 | Ohara Inc | Optical glass, optical element and preform |
| JP2013151411A (en) * | 2011-12-28 | 2013-08-08 | Ohara Inc | Optical glass, optical element and preform |
| JP2015205785A (en) * | 2014-04-17 | 2015-11-19 | 株式会社住田光学ガラス | Optical glass, preform for forming accurate press and optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774083B2 (en) | 1995-08-09 |
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