JPH0774083B2 - Fluorophosphate glass - Google Patents
Fluorophosphate glassInfo
- Publication number
- JPH0774083B2 JPH0774083B2 JP22131889A JP22131889A JPH0774083B2 JP H0774083 B2 JPH0774083 B2 JP H0774083B2 JP 22131889 A JP22131889 A JP 22131889A JP 22131889 A JP22131889 A JP 22131889A JP H0774083 B2 JPH0774083 B2 JP H0774083B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- total amount
- weight
- cation
- valence
- 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.)
- Expired - Fee Related
Links
- 239000005303 fluorophosphate glass Substances 0.000 title claims description 21
- 239000011521 glass Substances 0.000 claims description 34
- 150000001768 cations Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 239000006121 base glass Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000002222 fluorine compounds Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000005365 phosphate glass Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- -1 B 2 O 3 Inorganic materials 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- 229910017768 LaF 3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 230000035945 sensitivity Effects 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
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 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
- 229910005690 GdF 3 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004529 TaF 5 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
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 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
- 229910001632 barium fluoride Inorganic materials 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
- 238000005266 casting Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 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
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- TYIZUJNEZNBXRS-UHFFFAOYSA-K trifluorogadolinium Chemical compound F[Gd](F)F TYIZUJNEZNBXRS-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-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)
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。TECHNICAL FIELD The present invention relates to a fluorophosphate glass, for example, to a filter glass suitable for color correction of a color VTR camera.
［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。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。[Prior Art] Generally, the spectral sensitivity of light from an image pickup tube used in a color VTR camera extends from the visible region to the near-infrared region of 950 nm. Unless it is approximated to the visual sensitivity, the image becomes reddish and good color reproduction cannot be obtained. On the other hand, if the absorption on the ultraviolet side of the filter reaches the visible range, the image will become darker this time. Therefore, this type of filter is required to have a property of transmitting light of 400 to 520 nm as high as possible and absorbing light of 550 to 950 nm as much as possible. Conventionally, a glass obtained by adding CuO to phosphate glass has been used as a near-infrared absorption filter of this type.
［発明が解決しようとする課題］ 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A12O3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
をもつ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。[Problems to be Solved by the Invention] However, since the phosphate glass originally has poor weather resistance, it is disclosed in, for example, JP-A-62-128943 in order to improve it until it can be practically used. As such, addition of a relatively large amount of A 1 2 O 3 is required. As a result, the melting temperature rises, and the higher the temperature, the more easily copper ions tend to be reduced, so the divalent Cu 2+ ion of copper in the glass component having absorption in the near infrared region is reduced, There was a tendency for characteristic deterioration that the monovalent Cu + ion having absorption in the ultraviolet region was changed to lower the transmittance in the visible region and increase the transmittance in the infrared region. On the contrary, when trying to improve the transmittance characteristics, divalent Cu 2+ ions in the glass component are reduced to 1
Although the melting temperature will be lowered by adding an alkali metal oxide so as not to form valent Cu + ions, this will also further deteriorate the weather resistance of the glass itself. Therefore, when manufacturing a near-infrared absorption filter of this kind using a phosphate glass, the fact is that it has been practically provided by finding a compromise between the transmittance characteristic and the weather resistance, which are in a contradictory relationship.
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 object is to sufficiently satisfy the transmittance characteristics as a near-infrared absorption filter required for a color VTR filter, and sufficient for practical use. It is to provide a fluorophosphate glass having weather resistance capable of withstanding.
［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P2O5、１〜15％のA1F3、０〜9.9％のRF2（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RF2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（P2O5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。[Means for Solving the Problems] The present invention has been made to achieve the above object, and the fluorophosphate glass of the present invention is 0.5 to 38.5% by weight.
P 2 O 5 , 1 to 15% of A 1 F 3 , 0 to 9.9% of RF 2 (R is at least one selected from Ba, Sr, Ca, Mg, Zn and Pb, which are divalent metals. 0 to 23% of R'F (R 'is at least one selected from Li, Na and K which are monovalent metals having a valence of 1), and 1 to 33% of RF 2 and R'. F
The total amount of R ″ Fm is 0 to 68.5% (R ″ is at least one selected from La, Y, Gd, Si, B, Zr, Ta and Yb, which are metals having a valence of 3 to 5). , M is a number corresponding to the valence of R ″), and a metal oxide is represented by the formula y / (x + y) = 0.05 to 0.80 (where x is a metal oxide (excluding P 2 O 5 )). Is the total amount of
Is the total amount of all fluorides), and 100 parts by weight of basic glass containing 0.2%
˜15 parts by weight CuO.
本発明の弗燐酸塩ガラスは、耐候性悪化の原因となるP2
O5の量を比較的少量に抑えたものである。すなわち、P2
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、P2O5を0.5％未満とすると、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、A1F3
は耐候性を向上させるのに有効な成分であり、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A1F3は１〜15％の範囲に限
定される。また、２価成分RF2および１価成分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、量産時の成形に困難を
きたし、かつ耐候性を低下させる等の問題を発生させ
る。したがってRF2およびＲ′Ｆの合量は１〜33％の範
囲に限定される。ただし、RF2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、RF2のうち、BaF2,SrF2,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
０〜9.0％の範囲とするのが好ましい。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、この高原子価成分はその合量が6
8.5％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。ただし、高原子価成分Ｒ″Fm中のLaF3,YF3,G
dF3,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、B
F3、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。The fluorophosphate glass of the present invention contains P 2 which causes deterioration of weather resistance.
The amount of O 5 is kept relatively small. That is, P 2
The upper limit of O 5 is set to 38.5% to prevent deterioration of weather resistance. On the other hand, if P 2 O 5 is less than 0.5%, vitrification becomes difficult, so the lower limit of P 2 O 5 is made 0.5%. Also, A1F 3
Is an ingredient effective for improving weather resistance, and if it is less than 1%, its effect cannot be obtained, and if it exceeds 15%, the melting property of glass is lowered. Therefore A1F 3 is limited to a range from 1 to 15%. Further, the divalent component RF 2 and the monovalent component R′F are effective components for improving the melting property of the glass. If the total amount is less than 1%, it is difficult to vitrify, and if the total amount exceeds 33%, the glass becomes soft. This causes problems such as difficulty in molding during mass production and deterioration of weather resistance. Therefore, the total amount of RF 2 and R′F is limited to the range of 1 to 33%. However, if RF 2 exceeds 9.9%, the viscosity of the glass will drop too much, so R'F should be in the range of 0-9.9%.
If it exceeds 23%, the weather resistance will decrease, so it is limited to the range of 0-23%. Further, among RF 2 , BaF 2 , SrF 2 , PbF 2 each exceeds 9.9%, the viscosity of the glass is too low, so 0 to 9.9% range, CaF 2 , MgF 2 , ZnF 2 9.0% respectively. If it exceeds 0.1%, the viscosity of the glass is lowered too much, so that it is preferable to set it in the range of 0 to 9.0%. Further, if R'F which is LiF, NaF or KF exceeds 20%, the weather resistance is deteriorated, so that it is preferable to set it in the range of 0 to 20%. When 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 valence component is 6
If it exceeds 8.5%, the devitrification resistance of the glass deteriorates. Therefore, the total amount of the high valence components is limited to the range of 0 to 68.5%. However, LaF 3 , YF 3 , G in high valence component R ″ Fm
When dF 3 and YbF 3 exceed 60% respectively, devitrification is likely to occur, so it is preferable to set the range to 0 to 60%, and SiF 4 and B
If F 3 , ZrF 4 , and TaF 5 exceed 50%, devitrification tends to occur, so the range of 0 to 50% is preferable.
本発明の弗燐酸塩ガラスは、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（P2O5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 comprises a metal oxide represented by the formula y / (x + y) = 0.05 to 0.80 (where x is the total amount of the metal oxide (excluding P 2 O 5 ) and y
Is a total amount of all fluorides).
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。If y / (x + y) is less than 0.05 or exceeds 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R,R′,R″とし
て定義されたものが用いられる。As the metal species of the metal oxide, those defined as A1 and R, R ′, R ″ described above are used.
なお金属酸化物のうち、A12O3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,Gd2O3,Y2O3およびYb2O3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SiO2,B2O3,ZrO2およびTa2O5は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。またMgO,CaO,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Li2O,Na2O,K2O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。Note of the metal oxide, the A1 2 O 3 is meltability exceeds 10% worse, preferably in the range of 0%.
Further, when La 2 O 3 , Gd 2 O 3 , Y 2 O 3 and Yb 2 O 3 exceed 60%, the meltability deteriorates, so the range is preferably 0 to 60%. Further, if SiO 2 , B 2 O 3 , ZrO 2 and Ta 2 O 5 exceed 50%, devitrification tends to occur, so the range of 0 to 50% is preferable. Further, MgO, CaO, SrO and BaO are liable to devitrify when they exceed 60%, so that the range of 0 to 60% is preferable. Further, if Li 2 O, Na 2 O, and K 2 O exceed 20%, the weather resistance and devitrification resistance deteriorate, so the range is preferably from 0 to 20%.
本発明の弗燐酸塩ガラスは、上述のP2O5,A1F3,RF2,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。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。The fluorophosphate glass of the present invention has the above-mentioned P 2 O 5 , A1F 3 , RF 2 and R ′.
It contains 0.2 to 15 parts by weight of CuO based on 100 parts by weight of base glass containing F, R ″ Fm and metal oxide.
Is an essential component for near-infrared absorption, and CuO content is 0.2
The reason why the amount is limited to -15 parts by weight is that if it is less than 0.2 parts by weight, the absorption will be insufficient, while if it exceeds 15 parts by weight, the devitrification resistance of the glass will be deteriorated.
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。The particularly preferable composition of the fluorophosphate glass of the present invention is as follows.
基礎ガラスP2O5 ２〜37重量％ A1F3 １〜13重量％ RF2 ０〜9.9重量％ Ｒ′Ｆ ０〜20重量％ RF2＋Ｒ′Ｆ １〜33重量％ Ｒ″Fm ０〜65重量％ y/（ｘ＋ｙ） 0.10〜0.75 CuO 0.2〜13重量部（基礎ガラス100重量部に対して） ガラス技術分野においては、ガラスを構成する成分を上
述のように重量％で表示するとともにカチオン成分をカ
チオニック％で、アニオン成分をアニオニック％で表示
することがしばしば行われているので、後記表−１に記
載された実施例のNo.1〜11の弗燐酸塩ガラス組成に基づ
き好ましいカチオン成分の組成範囲をカチオニック％で
表示するとP5+3.3〜46.4％、A13+1.0〜18.1％、Ｒカチ
オン（原子価が２価の金属であるBa,Sr,Ca,Mg,Znおよび
Pbイオンの合量）1.1〜43.4％、Ｒ′カチオン（原子価
が１価の金属であるLi,NaおよびＫイオンの合量）０〜4
0.3％、ＲカチオンとＲ′カチオンの合量4.3〜53.3％、
Ｒ″カチオン（原子価が３〜５価の金属であるLa,Y,Gd,
Si,B,Zr,TaおよびYbイオンの合量）０〜31.2％であり、
かつCu2+が基礎ガラスの全カチオン成分の合量に対して
0.56〜15.50％である。また好ましいアニオン成分の組
成範囲をアニオニック％で表示するとF-6.9〜51.7％で
ある。Base glass P 2 O 5 2~37 wt% A1F 3 1 to 13 wt% RF 2 0 to 9.9 wt% R'f 0 to 20 wt% RF 2 + R'F 1~33 wt% R "Fm 0 to 65 weight % Y / (x + y) 0.10 to 0.75 CuO 0.2 to 13 parts by weight (relative to 100 parts by weight of basic glass) In the glass technical field, the components constituting the glass are expressed as% by weight as described above and the cation component is Since the anion component is often expressed as anionic percentage in Cationic%, the composition of the preferred cationic component is based on the fluorophosphate glass compositions of Nos. 1 to 11 in Examples described in Table 1 below. When the range is expressed in Cationic%, P 5+ 3.3 to 46.4%, A 1 3+ 1.0 to 18.1%, R cation (Ba, Sr, Ca, Mg, Zn and valence divalent metals and
Pb ion total amount) 1.1 to 43.4%, R'cation (total amount of monovalent metal Li, Na and K ions) 0 to 4
0.3%, total amount of R cation and R'cation 4.3 to 53.3%,
R ″ cation (La, Y, Gd, which is a metal having a valence of 3 to 5)
Si, B, Zr, Ta and Yb ions) 0-31.2%,
And Cu 2+ is based on the total amount of all cation components of the basic glass
It is 0.56 to 15.50%. When the composition range of the preferable anion component is expressed in anionic%, it is F - 6.9 to 51.7%.
［実施例］ 以下実施例により本発明を更に説明する。[Examples] The present invention will be further described 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、弗化イットリウム、弗化ガドリニ
ウム、弗化バリウム、酸化第２銅を所定量混合し（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、攪拌して脱泡、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YF3,12.8％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100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。Examples 1 to 11 As a raw material, orthophosphoric acid aqueous solution, barium carbonate, aluminum fluoride, lanthanum fluoride, yttrium fluoride, gadolinium fluoride, barium fluoride, cupric oxide were mixed in a predetermined amount (as a raw material, aluminum phosphate, It does not prevent the use of complex salts such as barium phosphate), with a platinum crucible, cover and melt at 800-900 ° C, stir to defoam and homogenize, then add to a preheated mold By casting and slow cooling,
21.4% P 2 O 5 , 1.5% A 1 F 3 and 9.5% BaF 2 , 7.5% by weight
% LaF 3 , 14.7% YF 3 , 12.8% GdF 3 and 32.6% BaO
A fluorophosphate glass of Example 1 was obtained which contained 1.45 parts by weight of CuO in 100 parts by weight of the base glass having y / (x + y) of 0.59.
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。In the same manner as above, fluorophosphate glasses of Examples 2 to 11 were obtained.
The compositions of the fluorophosphate glasses of Examples 1 to 11 are summarized in Table 1.
なお上述のようにガラス研究者の間で、ガラスを構成す
る成分をカチオン成分及びアニオン成分に分け、これら
の量をカチオニック％及びアニオニック％で表示するこ
とが、各カチオン成分及びアニオン成分の存在量の比較
等の都合上便利であり、広く採用されているので、表−
１には各弗燐酸塩ガラスについて重量％表示とカチオニ
ック％及びアニオニック％表示とを併記した。表−２に
実施例の組成No.1のガラス組成について重量％からカチ
オニック％及びアニオニック％へ換算した例を示す。As mentioned above, it is possible for glass researchers to divide the components that make up the glass into cation components and anion components and display these amounts in terms of Cationic% and Anionic% to determine the amount of each cation and anion component present. It is convenient for comparison and is widely adopted.
In Table 1, the weight% indication and the cationic% and anionic% indications are shown for each fluorophosphate glass. Table 2 shows an example in which the glass composition of composition No. 1 of the example is converted from wt% to Cationic% and Anionic%.
なお、表−１において、特定のカチオンが弗化物に由来
するカチオンと酸化物に由来するカチオンがあるときは
当該カチオンの弗化物と併記されたカチオン欄にまとめ
て記載した。In Table 1, when specific cations include cations derived from fluoride and cations derived from oxide, they are collectively described in the column of cations together with the fluoride of the cation.
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950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 glass of Examples 1 to 11 thus obtained was evaluated by keeping the polished glass under constant temperature and constant humidity conditions of about 65 ° C. and 90% relative humidity at regular intervals. It was evaluated by observing the surface state of the glass and determining the time until the glass surface was altered. As a result, as shown in Table 1, in the fluorophosphate glass of Example 1, the time until the glass surface was altered was 980 hours, and the weather resistance was extremely excellent. Also, in the fluorophosphate glasses of Examples 2 to 11, the time until the glass surface was altered was 950 hours or more (10 hours in the fluorophosphate glasses of Examples 5, 7, and 9). It was extremely excellent in 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P2O5と比較的多量のA12O3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
全に白く変質し、ガラスの透明度を失うに至った。On the other hand, the phosphate glass of Comparative Examples 1 and 2 corresponding to the phosphate glass described in JP-A-62-128943 (70% or more of P 2 O 5 and a relatively large amount of A 1 2 O 3 Table 1
As shown in Fig. 2, the deterioration time of the glass surface was 240 hours and 216 hours, respectively, and after about 800 hours, it became completely white and the transparency of the glass was lost.
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しく優れていることが明らか
となった。From the above, it became clear that the fluorophosphate glass of the present invention is significantly superior in weather resistance to the conventional phosphate glass.
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
く、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, FIG. 1 shows the spectral transmittance curves of the glasses of Examples 1, 3, 11 and Comparative Examples 1, 2. The thickness of the glass used for the measurement is 1.6 mm. As is clear from the figure, Examples 1, 3, 11
The glass is a phosphate-based comparative example 1, which does not contain fluoride.
It has a higher transmittance in the wavelength of 360 to 500 nm than the glass of 2 and has excellent spectral transmittance as a filter for a color VTR camera that sufficiently absorbs light of 550 to 950 nm on the longer wavelength side. It became clear.
［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。 [Effects of the Invention] As described above, according to the present invention, there is provided a fluorophosphate glass having extremely excellent weather resistance, which has not been obtained conventionally, and at the same time, 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 a conventional phosphate glass.
Claims (2)
1F3、０〜9.9％のRF2（Ｒは原子価が２価の金属であるB
a,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RF2およびは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（P2O5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% to 38.5% by weight of P 2 O 5 and 1% to 15% of A.
1F 3 , 0-9.9% RF 2 (R is a divalent metal B
at least one selected from a, Sr, Ca, Mg, Zn and Pb), 0 to 23% of R'F (R 'is selected from Li, Na and K which are monovalent metals having a valence of 1) At least one), 1 to 33% of RF 2 and is the total amount of R'F, 0 to 68.5
% R ″ Fm (R ″ is a metal with a valence of 3 to 5 La,
Y is at least one selected from Y, Gd, Si, B, Zr, Ta and Yb, m is a number corresponding to the valence of R ″), and a metal oxide is represented by the formula y / (x + y ) = 0.05 to 0.80 (where x is the total amount of metal oxides (excluding P 2 O 5 ), y
Is the total amount of all fluorides), and 100 parts by weight of basic glass containing 0.2%
A fluorophosphate glass, characterized in that it contains ˜15 parts by weight of CuO.
0〜18.1％、Ｒカチオン（原子価が２価の金属であるBa,
Sr,Ca,Mg,ZnおよびPbイオンの合量）1.1〜43.4％Ｒ′カ
チオン（原子価が１価の金属であるLi,NaおよびＫイオ
ンの合量）０〜40.3％、ＲカチオンとＲ′カチオンの合
量4.3〜53.3％、Ｒ″カチオン（原子価が３〜５価の金
属であるLa,Y,Gd,Si,B,Zr,TaおよびYbイオンの合量）０
〜31.2％を含み、かつCu2+を基礎ガラスの全カチオン成
分の合量に対して0.56〜15.50％を含み、一方アニオニ
ック％でF-を6.9〜51.7％含むことを特徴とする弗燐酸
塩ガラス。2. Cationic% P 5+ 3.3 to 46.4%, A 1 3+ 1.
0 to 18.1%, R cation (Ba, which is a divalent metal,
Sr, Ca, Mg, Zn and Pb ions total) 1.1 to 43.4% R'cation (total amount of monovalent metal Li, Na and K ions) 0 to 40.3%, R cation and R ′ Total amount of cations is 4.3 to 53.3%, R ″ cation (total amount of La, Y, Gd, Si, B, Zr, Ta and Yb ions, which are metal having a valence of 3 to 5) 0
Comprises ～31.2%, and comprises an 0.56 to 15.50% relative to the total amount of all cationic components of the base glass to Cu 2+, whereas F by anionic% - fluoride phosphate, characterized in that it comprises a 6.9 to 51.7% Glass.
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 JPH0383835A (en) | 1991-04-09 |
| JPH0774083B2 true 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923950A (en) * | 2011-08-11 | 2013-02-13 | Hoya株式会社 | Fluorophosphate glass and method for producing the same and near-infrared absorbing filter |
| CN103708727A (en) * | 2012-09-29 | 2014-04-09 | 成都光明光电股份有限公司 | Fluophosphate optical glass |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617347A (en) * | 2003-04-09 | 2005-05-18 | Hoya株式会社 | Glass for semiconductor package window, used glass window and its manufacturing method, and semiconductor package |
| JP4652941B2 (en) * | 2005-09-30 | 2011-03-16 | Ｈｏｙａ株式会社 | Lens and manufacturing method thereof |
| JP5801773B2 (en) * | 2011-08-11 | 2015-10-28 | Hoya株式会社 | Fluorophosphate glass, method for producing the same, and near infrared light absorption filter |
| JP6174317B2 (en) * | 2011-12-28 | 2017-08-02 | 株式会社オハラ | Optical glass, optical element and preform |
| JP2013151410A (en) * | 2011-12-28 | 2013-08-08 | Ohara Inc | Optical glass, optical element and preform |
| JP5927227B2 (en) * | 2014-04-17 | 2016-06-01 | 株式会社住田光学ガラス | Optical glass, precision press-molding preform, and optical element |
-
1989
- 1989-08-28 JP JP22131889A patent/JPH0774083B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923950A (en) * | 2011-08-11 | 2013-02-13 | Hoya株式会社 | Fluorophosphate glass and method for producing the same and near-infrared absorbing filter |
| CN103708727A (en) * | 2012-09-29 | 2014-04-09 | 成都光明光电股份有限公司 | Fluophosphate optical glass |
| CN103708727B (en) * | 2012-09-29 | 2016-08-03 | 成都光明光电股份有限公司 | Fluorophosphate optical glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0383835A (en) | 1991-04-09 |
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