JPH09100136A - Near infrared absorbing filter glass - Google Patents
Near infrared absorbing filter glassInfo
- Publication number
- JPH09100136A JPH09100136A JP19105596A JP19105596A JPH09100136A JP H09100136 A JPH09100136 A JP H09100136A JP 19105596 A JP19105596 A JP 19105596A JP 19105596 A JP19105596 A JP 19105596A JP H09100136 A JPH09100136 A JP H09100136A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- filter glass
- infrared absorption
- composition range
- absorption filter
- 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.)
- Withdrawn
Links
- 239000011521 glass Substances 0.000 title claims abstract description 88
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 60
- 238000010521 absorption reaction Methods 0.000 claims description 29
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 11
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 6
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical group 0.000 abstract description 4
- 239000005365 phosphate glass Substances 0.000 abstract description 2
- 229910011763 Li2 O Inorganic materials 0.000 abstract 1
- 229910004742 Na2 O Inorganic materials 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 23
- 238000002834 transmittance Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 238000004031 devitrification Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- VUDJAFZYSMINQA-UHFFFAOYSA-L zinc metaphosphate Chemical compound [Zn+2].[O-]P(=O)=O.[O-]P(=O)=O VUDJAFZYSMINQA-UHFFFAOYSA-L 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
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は近赤外吸収フィルタ
ーガラスに係り、詳しくは４００〜６００ｎｍの光を高
透過し、６００ｎｍ付近からの近赤外光を選択的に吸収
する分光特性を有し、特にカラーＶＴＲカメラの色補正
のために利用されるフィルターガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared absorption filter glass, and more particularly, it has a spectral characteristic of highly transmitting light of 400 to 600 nm and selectively absorbing near-infrared light from around 600 nm. , Especially for filter glasses used for color correction of color VTR cameras.
【０００２】[0002]
【従来の技術】近赤外吸収フィルターガラスは、従来か
ら種々検討され実用化されてきている。2. Description of the Related Art Various types of near-infrared absorption filter glass have been studied and put to practical use.
【０００３】例えば特開昭６２−１２８９４３号公報に
は、重量％で６０〜９０％のＰ2Ｏ5、７．５〜２０％の
Ａｌ2Ｏ3 、０〜１５％のＢ2Ｏ3＋ＳｉＯ2、１〜２５％
のＢａＯ＋ＭｇＯ＋ＣａＯ＋ＳｒＯ、０〜１５％Ｙ2Ｏ3
＋Ｌａ2Ｏ3＋ＺｒＯ2＋Ｔａ2Ｏ5＋ＴｉＯ2、０〜１０％
のＰｂＯ、０．４〜１５．０％のＣｕＯからなるカラー
ドガラスが開示されている。For example, in JP-A-62-128943, 60 to 90% by weight of P 2 O 5 , 7.5 to 20% of Al 2 O 3 and 0 to 15% of B 2 O 3 + SiO are disclosed. 2 , 1-25%
BaO + MgO + CaO + SrO, 0-15% Y 2 O 3
+ La 2 O 3 + ZrO 2 + Ta 2 O 5 + TiO 2 , 0 to 10%
Of PbO and 0.4 to 15.0% CuO are disclosed.
【０００４】又、特開平４−１０４９１８号公報には重
量％で、６０〜８０％のＰ2Ｏ5 、３〜１１％のＡｌ2Ｏ
3 、３〜９．５％のＢａＯ、３〜２０％のＭｇＯ＋Ｃａ
Ｏ＋ＢａＯ＋ＳｒＯ、１〜５．５％のＬｉ2Ｏ、１〜１
０％のＬｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ、０〜５％のＳｉＯ2＋
Ｂ2Ｏ3 、０〜５％のＺｒＯ2＋ＴｉＯ2＋Ｙ2Ｏ3＋Ｌａ2
Ｏ3 、０．２〜１０％のＣｕＯからなる燐酸塩ガラスス
が開示されている。Further, in Japanese Patent Application Laid-Open No. 4-104918, 60 to 80% of P 2 O 5 and 3 to 11% of Al 2 O are contained by weight.
3 , 3 to 9.5% BaO, 3 to 20% MgO + Ca
O + BaO + SrO, 1~5.5% of Li 2 O, 1 to 1
0% Li 2 O + Na 2 O + K 2 O, 0-5% SiO 2 +
B 2 O 3, 0~5% of ZrO 2 + TiO 2 + Y 2 O 3 + La 2
O 3, phosphate Garasusu discloses consisting from 0.2 to 10% of CuO.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら特開昭６
２−１２８９４３号公報および特開平４−１０４９１８
号公報に開示されているガラスは、Ｐ2Ｏ5を多量に含有
するため化学的耐久性が低く長期間の使用が困難であ
る。また化学的耐久性を改善すべくＡｌ2Ｏ3を比較的多
量含有させると溶融温度が上昇し、その結果Ｃｕ2+が還
元され、紫外域に吸収をもつＣｕ+イオンにより４００
ｎｍ付近の透過率が低いという問題があった。SUMMARY OF THE INVENTION However, Japanese Unexamined Patent Publication No.
2-128943 and JP-A-4-104918.
Since the glass disclosed in Japanese Patent Publication contains a large amount of P 2 O 5 , it has low chemical durability and is difficult to use for a long period of time. When a relatively large amount of Al 2 O 3 is added to improve chemical durability, the melting temperature rises, and as a result Cu 2+ is reduced, and Cu + ions having an absorption in the ultraviolet region cause 400
There is a problem that the transmittance in the vicinity of nm is low.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記問題点
を解決すべく鋭意研究した結果、ＣｕＯを含む燐酸塩系
近赤外吸収ガラスを得ようとした場合、Ｐ2Ｏ5が３５〜
５０％の組成域において、ＺｎＯを比較的に多量に含有
させ、アルカリ金属酸化物を適量添加することにより、
近赤外吸収フィルターとして有用な４００〜６００ｎｍ
における高透過特性と６００ｎｍ以上におけるシャープ
な吸収特性とを有し、かつ熱膨張係数が小さく、化学的
耐久性が良いガラスが得られることを見い出した。As a result of intensive studies to solve the above problems, the present inventors have found that when a phosphate-based near-infrared absorbing glass containing CuO is obtained, P 2 O 5 is 35%. ~
In a composition range of 50%, ZnO is contained in a relatively large amount, and an appropriate amount of alkali metal oxide is added,
400 ~ 600nm useful as near infrared absorption filter
It has been found that a glass having a high transmission property in (1) and a sharp absorption property in 600 nm or more, a small thermal expansion coefficient, and a good chemical durability can be obtained.
【０００７】本発明はこの知見に基づいて完成されたも
のであり、重量％で Ｐ2Ｏ5 ３５〜５０％ Ｌｉ2Ｏ ０〜５％ Ｎａ2Ｏ ０〜１２％ Ｋ2Ｏ ０〜２０％ Ｃｓ2Ｏ ０〜２０％ Ｒ2Ｏ（Ｒはアルカリ金属である） １．５〜２０％ ＺｎＯ １７〜４８％ ＭｇＯ ０〜７％ ＣａＯ ０〜７％ ＳｒＯ ０〜７％ ＢａＯ ０〜１２％ Ｒ′Ｏ（Ｒ′はアルカリ土類金属である） ０〜１５％ ＣｕＯ ０．２〜１２％ を含むことを特徴とする近赤外吸収フィルターガラスを
要旨とする。The present invention has been completed on the basis of this finding, and in weight%, P 2 O 5 35 to 50% Li 2 O 0 to 5% Na 2 O 0 to 12% K 2 O 0 to 20% Cs 2 O 0 to 20% R 2 O (R is an alkali metal) 1.5 to 20% ZnO 17 to 48% MgO 0 to 7% CaO 0 to 7% SrO 0 to 7% BaO 0 to 12% R The subject matter is a near-infrared absorption filter glass characterized by containing 0'R (R 'is an alkaline earth metal) 0 to 15% CuO 0.2 to 12%.
【０００８】[0008]
【発明の実施の形態】本発明の近赤外吸収フィルターガ
ラスは、Ｐ2Ｏ5を３５〜５０％、Ｌｉ2Ｏを０〜５％、
Ｎａ2Ｏを０〜１２％、Ｋ2Ｏを０〜２０％、Ｃｓ2Ｏを
０〜２０％、Ｒ2Ｏ（Ｒはアルカリ金属である）を１．
５〜２０％、ＺｎＯを１７〜４８％、ＣｕＯを０．２〜
１２％含むことを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The near-infrared absorption filter glass of the present invention contains 35 to 50% of P 2 O 5 , 0 to 5% of Li 2 O,
Na 2 O is 0 to 12%, K 2 O is 0 to 20%, Cs 2 O is 0 to 20%, and R 2 O (R is an alkali metal) is 1.
5-20%, ZnO 17-48%, CuO 0.2-
It is characterized by containing 12%.
【０００９】各成分の組成を上述のような数値範囲に限
定した理由は次のとおりである。The reason why the composition of each component is limited to the above numerical range is as follows.
【００１０】本発明の近赤外吸収フィルターガラスにお
いて、Ｐ2Ｏ5は４００〜６００ｎｍにおける透過率を高
め、Ｃｕ2+による７００ｎｍ以上の波長域での吸収をシ
ャープに変化させるためには最も好ましいガラス網目形
成成分であるが、その含有量が３５％未満では所望の透
過特性が得られないばかりでなく、ガラスの結晶化傾向
が強くなり安定した製造が困難になる。また５０％を超
えると化学的耐久性が急激に悪化し本発明の目的とする
ガラスが得られなくなる。従ってＰ2Ｏ5の組成範囲は３
５〜５０％に限定される。Ｐ2Ｏ5の組成範囲は３７〜４
９％が好ましく、４０〜４８％が特に好ましい。In the near-infrared absorption filter glass of the present invention, P 2 O 5 is most preferable for enhancing the transmittance in the range of 400 to 600 nm and sharply changing the absorption of Cu 2+ in the wavelength range of 700 nm or more. Although it is a glass network-forming component, if its content is less than 35%, not only the desired transmission characteristics cannot be obtained, but also the glass tends to crystallize and stable production becomes difficult. Further, if it exceeds 50%, the chemical durability is drastically deteriorated and the glass intended by the present invention cannot be obtained. Therefore, the composition range of P 2 O 5 is 3
It is limited to 5 to 50%. The composition range of P 2 O 5 is 37 to 4
9% is preferable and 40-48% is especially preferable.
【００１１】本発明の近赤外吸収フィルターガラスにお
いて、Ｋ2Ｏは耐失透性を良化させ、且つガラスの熔解
性を向上させる成分であるが、２０％を上回ると化学的
耐久性が悪化し又熱膨張係数も大きくなる。従ってＫ2
Ｏの組成範囲は０〜２０％に限定される。Ｋ2Ｏの組成
範囲は０〜１７％が好ましい。In the near-infrared absorption filter glass of the present invention, K 2 O is a component that improves the devitrification resistance and improves the meltability of the glass, but if it exceeds 20%, the chemical durability is increased. It also deteriorates and the coefficient of thermal expansion increases. Therefore K 2
The composition range of O is limited to 0 to 20%. The composition range of K 2 O is preferably 0 to 17%.
【００１２】本発明の近赤外吸収フィルターガラスは、
アルカリ金属酸化物として上述のＫ2Ｏ以外にＬｉ2Ｏ、
Ｎａ2ＯおよびＣｓ2Ｏを必要に応じて含有することがで
きる。The near infrared absorption filter glass of the present invention comprises:
Li 2 O in addition to the above-mentioned K 2 O as alkali metal oxide,
If necessary, Na 2 O and Cs 2 O can be contained.
【００１３】Ｌｉ2Ｏ、Ｎａ2Ｏ、Ｃｓ2Ｏはガラスの熔
解性を向上させ、透過特性を良化する成分であるが、そ
れぞれ５％、１２％、２０％を超えると化学的耐久性が
悪化し又結晶化傾向が強くなる。従ってＬｉ2Ｏの組成
範囲は０〜５％、Ｎａ2Ｏの組成範囲は０〜１２％、Ｃ
ｓ2Ｏの組成範囲は０〜２０％に限定される。Ｌｉ2Ｏの
組成範囲は０〜３％が好ましい。Ｎａ2Ｏの組成範囲は
０〜８％が好ましく、０〜６％が特に好ましい。Ｃｓ2
Ｏの組成範囲は０〜１７％が好ましく、０〜１５％が特
に好ましい。Li 2 O, Na 2 O, and Cs 2 O are components that improve the meltability of glass and improve the transmission characteristics, but if they exceed 5%, 12%, and 20%, respectively, the chemical durability is increased. And the tendency to crystallize becomes stronger. Therefore, the composition range of Li 2 O is 0 to 5%, the composition range of Na 2 O is 0 to 12%, and C
The composition range of s 2 O is limited to 0 to 20%. The composition range of Li 2 O is preferably 0 to 3%. The composition range of Na 2 O is preferably 0 to 8%, particularly preferably 0 to 6%. Cs 2
The composition range of O is preferably 0 to 17%, particularly preferably 0 to 15%.
【００１４】本発明の近赤外吸収フィルターガラスにお
いては、アルカリ金属酸化物の合量も限定され、Ｒ2Ｏ
（Ｒはアルカリ金属である）の組成範囲は１．５〜２０
％である。Ｒ2Ｏが１．５％未満では、結晶化傾向が強
くなり、一方２０％を超えると、化学的耐久性が悪化
し、また熱膨張係数が大きくなる。Ｒ2Ｏの組成範囲
は、２〜１７％が好ましい。In the near infrared absorption filter glass of the present invention, the total amount of alkali metal oxides is also limited, and R 2 O
The composition range of (R is an alkali metal) is 1.5 to 20.
%. When R 2 O is less than 1.5%, the crystallization tendency becomes strong, while when it exceeds 20%, the chemical durability is deteriorated and the thermal expansion coefficient is increased. The composition range of R 2 O is preferably 2 to 17%.
【００１５】本発明の近赤外吸収フィルターガラスにお
いて、Ｋ2Ｏは、他のアルカリ金属酸化物と比較して化
学的耐久性を大きく損なうことなく耐失透性を高める効
果が強い。従って低い熔解温度を必要とする特別な場合
を除いて、アルカリ金属酸化物としてＫ2Ｏのみを１．
５〜１７％の範囲で使用するのが特に好ましい。In the near-infrared absorption filter glass of the present invention, K 2 O has a strong effect of improving devitrification resistance without greatly impairing chemical durability as compared with other alkali metal oxides. Therefore, except for special cases where a low melting temperature is required, only K 2 O as an alkali metal oxide is added to 1.
It is particularly preferably used in the range of 5 to 17%.
【００１６】本発明の近赤外吸収フィルターガラスにお
いて、ＺｎＯは化学的耐久性の良化、熱膨張係数の抑
制、熔解性の良化などの効果を有する必須の成分である
が、１７％未満であるとこれらの効果が得られず、一方
４８％を超えると結晶化傾向が強くなり、安定したガラ
ス製造ができにくくなる。従ってＺｎＯの組成範囲は１
７〜４８％に限定される。ＺｎＯの組成範囲は２５〜４
５％が好ましく、２７〜４２％が特に好ましい。In the near-infrared absorption filter glass of the present invention, ZnO is an essential component having the effects of improving chemical durability, suppressing thermal expansion coefficient, improving meltability, etc., but less than 17%. If these values are not obtained, on the other hand, if it exceeds 48%, the tendency of crystallization becomes strong and stable glass production becomes difficult. Therefore, the composition range of ZnO is 1
Limited to 7-48%. The composition range of ZnO is 25 to 4
5% is preferable and 27-42% is especially preferable.
【００１７】本発明の近赤外吸収フィルターガラスにお
いて、ＣｕＯは近赤外を吸収するための必須成分であ
り、０．２％以上の添加により透過率を調整することが
可能である。しかしながら１２％を上回ると結晶化傾向
が強まり安定に量産することが困難となる。従ってＣｕ
Ｏの組成範囲は０．２〜１２％に限定される。ＣｕＯの
組成範囲は、０．２〜１０％が好ましく、０．２〜８％
が特に好ましい。In the near-infrared absorption filter glass of the present invention, CuO is an essential component for absorbing near-infrared light, and its transmittance can be adjusted by adding 0.2% or more. However, if it exceeds 12%, the tendency of crystallization becomes strong, and it becomes difficult to mass-produce it stably. Therefore Cu
The composition range of O is limited to 0.2 to 12%. The composition range of CuO is preferably 0.2 to 10%, and 0.2 to 8%
Is particularly preferred.
【００１８】本発明の赤外吸収フィルターガラスにおい
て、Ａｓ2Ｏ3は必須成分ではないが、Ｃｕ2+を安定に保
つために有効な成分であり、４００nm付近の透過率の向
上に効果がある。特に組成中のアルカリ金属酸化物の含
量が１２mol％を下回る時はＡｓ2Ｏ3を添加した方がよ
い。その添加量は６wt％を上回ると結晶化傾向が強まる
ばかりでなく、化学的耐久性が悪化する。従ってＡｓ2
Ｏ3の組成範囲は０〜６％に限定され、０．０５〜５％
が特に好ましい。In the infrared absorption filter glass of the present invention, As 2 O 3 is not an essential component, but it is an effective component for keeping Cu 2+ stable and is effective in improving the transmittance around 400 nm. . Especially when the content of the alkali metal oxide in the composition is less than 12 mol%, it is better to add As 2 O 3 . If the amount added exceeds 6 wt%, not only the crystallization tendency will be strengthened, but also the chemical durability will be deteriorated. Therefore As 2
The composition range of O 3 is limited to 0 to 6%, 0.05 to 5%
Is particularly preferred.
【００１９】Ｂ2Ｏ3は化学的耐久性の向上を目的として
１０％まで含有することができるが、１０％を超えると
所望の透過特性が得られなくなるばかりでなく、逆に化
学的耐久性が悪化する。従ってＢ2Ｏ3の組成範囲は０〜
１０％に限定される。Ｂ2Ｏ3の組成範囲は０〜８％が好
ましい。B 2 O 3 can be contained up to 10% for the purpose of improving the chemical durability, but if it exceeds 10%, not only the desired permeation characteristics will not be obtained, but conversely, the chemical durability will be impaired. Becomes worse. Therefore, the composition range of B 2 O 3 is 0 to
Limited to 10%. The composition range of B 2 O 3 is preferably 0 to 8%.
【００２０】Ａｌ2Ｏ3 は化学的耐久性を良化させる成
分であり、５％まで添加できるが、５％を上回ると結晶
化傾向が強くなり、またガラスの熔解性が悪化する。従
ってＡｌ2Ｏ3の組成範囲は０〜５％に限定される。Ａｌ
2Ｏ3の組成範囲は、０．５〜３％が好ましい。Al 2 O 3 is a component that improves the chemical durability and can be added up to 5%, but if it exceeds 5%, the crystallization tendency becomes strong and the meltability of glass deteriorates. Therefore, the composition range of Al 2 O 3 is limited to 0 to 5%. Al
The composition range of 2 O 3 is preferably 0.5 to 3%.
【００２１】ＭｇＯ、ＣａＯ、ＳｒＯは少量の添加で化
学的耐久性を良化させるが、それぞれ７％を上回るとガ
ラスの熔解性及び失透性が悪化する。従ってＭｇＯの組
成範囲は０〜７％、ＣａＯの組成範囲は０〜７％、Ｓｒ
Ｏの組成範囲は０〜７％に限定されるが、いずれも０〜
５％であるのが好ましい。MgO, CaO and SrO improve the chemical durability with a small amount of addition, but if they exceed 7% each, the meltability and devitrification of the glass deteriorate. Therefore, the composition range of MgO is 0 to 7%, the composition range of CaO is 0 to 7%, and Sr
The composition range of O is limited to 0 to 7%, but all are 0 to
Preferably it is 5%.
【００２２】ＢａＯは少量の添加で特に耐失透性を改善
する効果がある。しかしながら、１２％を上回るとガラ
スの熔解性が悪化する。従ってＢａＯの組成範囲は０〜
１２％に限定される。ＢａＯの組成範囲は０〜８％であ
るのが好ましい。BaO has an effect of improving the devitrification resistance especially when added in a small amount. However, if it exceeds 12%, the meltability of glass deteriorates. Therefore, the composition range of BaO is 0 to
Limited to 12%. The composition range of BaO is preferably 0 to 8%.
【００２３】上述のＭｇＯ、ＣａＯ、ＳｒＯおよびＢａ
Ｏはアルカリ土類金属酸化物に含まれるものであるが、
本発明の近赤外吸収フィルターガラスにおいてはアルカ
リ土類金属酸化物の合量も重要であり、Ｒ′Ｏ（Ｒ′は
アルカリ土類金属である）の組成範囲は０〜１５％に限
定される。その理由は、Ｒ′Ｏの量が１５％を上回ると
ガラスの熔解性が悪化し、また化学的耐久性も悪化する
からである。Ｒ′Ｏの組成範囲は、０．５〜１０％が好
ましい。The above-mentioned MgO, CaO, SrO and Ba
O is contained in the alkaline earth metal oxide,
In the near infrared absorption filter glass of the present invention, the total amount of alkaline earth metal oxides is also important, and the composition range of R'O (R 'is an alkaline earth metal) is limited to 0 to 15%. It The reason is that if the amount of R'O exceeds 15%, the meltability of the glass deteriorates and the chemical durability also deteriorates. The composition range of R'O is preferably 0.5 to 10%.
【００２４】ＰｂＯはＺｎＯと同様の効果があり、Ｚｎ
Ｏから２５％まで置換することができるが、化学的耐久
性を良化させる効果はＺｎＯより小さく、２５％を上回
ると本発明の目的とする化学的耐久性が得られない。従
ってＰｂＯの組成範囲は０〜２５％に限定される。Ｐｂ
Ｏの組成範囲は０〜２０が好ましい。PbO has the same effect as ZnO.
Although it is possible to substitute from O to 25%, the effect of improving the chemical durability is smaller than that of ZnO, and if it exceeds 25%, the chemical durability aimed at by the present invention cannot be obtained. Therefore, the composition range of PbO is limited to 0 to 25%. Pb
The composition range of O is preferably 0 to 20.
【００２５】Ｌａ2Ｏ3 、Ｙ2Ｏ3 、Ｇｄ2Ｏ3 、Ｂｉ2Ｏ
3 はいずれも少量の添加で化学的耐久性を良化させる
が、Ｌａ2Ｏ3 、Ｙ2Ｏ3 、Ｇｄ2Ｏ3 がそれぞれ３％、
Ｂｉ2Ｏ3が５％を上回ると結晶化傾向が強まり安定な製
造が困難になる。よってＬａ2Ｏ3、Ｙ2Ｏ3、Ｇｄ2Ｏ3の
組成範囲はそれぞれ０〜３％、Ｂｉ2Ｏ3の組成範囲は０
〜５％に限定される。Ｌａ2Ｏ3、Ｙ2Ｏ3、Ｇｄ2Ｏ3の組
成範囲はそれぞれ０〜２％が好ましく、Ｂｉ2Ｏ3の組成
範囲は０〜４％が好ましい。La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Bi 2 O
All of 3 improve chemical durability by adding a small amount, but La 2 O 3 , Y 2 O 3 and Gd 2 O 3 are 3% each,
If Bi 2 O 3 exceeds 5%, the tendency of crystallization becomes strong and stable production becomes difficult. Therefore, the composition range of La 2 O 3 , Y 2 O 3 , and Gd 2 O 3 is 0 to 3%, and the composition range of Bi 2 O 3 is 0.
Limited to ~ 5%. The composition range of La 2 O 3 , Y 2 O 3 , and Gd 2 O 3 is preferably 0 to 2%, and the composition range of Bi 2 O 3 is preferably 0 to 4%.
【００２６】Ｉｎ2Ｏ3は少量の添加により特に化学的耐
久性を良化させるが、７％を上回ると結晶化傾向が強ま
る。従ってＩｎ2Ｏ3の組成範囲は０〜７％に限定され、
好ましくは０〜５％である。When In 2 O 3 is added in a small amount, the chemical durability is particularly improved, but if it exceeds 7%, the crystallization tendency becomes stronger. Therefore, the composition range of In 2 O 3 is limited to 0 to 7%,
It is preferably 0 to 5%.
【００２７】Ｓｃ2Ｏ3はＩｎ2Ｏ3と同様に少量の添加に
より特に化学的耐久性を良化させるが、５％を上回ると
結晶化傾向が強まる。従ってＳｃ2Ｏ3の組成範囲は０〜
５％に限定され、好ましくは０〜４％である。Similar to In 2 O 3 , Sc 2 O 3 improves the chemical durability particularly by adding in a small amount, but if it exceeds 5%, the crystallization tendency becomes stronger. Therefore, the composition range of Sc 2 O 3 is 0 to
It is limited to 5%, preferably 0 to 4%.
【００２８】ＳｉＯ2、ＴｉＯ2、ＺｒＯ2、Ｎｂ2Ｏ5、
Ｔａ2Ｏ5等の成分はいずれも化学的耐久性を良化させる
成分であるが、ＳｉＯ2、ＴｉＯ2、ＺｒＯ2は３％、Ｎ
ｂ2Ｏ5、Ｔａ2Ｏ5は７％を上回るとガラス熔解の際に溶
け残りやすく、熔解温度を昇温させる必要が生じ、その
結果Ｃｕ2+を安定にすることが難しくなる。従ってＳｉ
Ｏ2、ＴｉＯ2、ＺｒＯ2の組成範囲はそれぞれ０〜３％
に限定され、Ｎｂ2Ｏ5の組成範囲は０〜５％に限定さ
れ、Ｔａ2Ｏ5の組成範囲は０〜７％に限定される。Ｓｉ
Ｏ2、ＴｉＯ2、ＺｒＯ2の組成範囲はそれぞれ０〜２％
が好ましく、Ｎｂ2Ｏ5の組成範囲は０〜３％が好まし
く、Ｔａ2Ｏ5の組成範囲は０〜５％が好ましい。SiO 2 , TiO 2 , ZrO 2 , Nb 2 O 5 ,
All of the components such as Ta 2 O 5 improve the chemical durability, but SiO 2 , TiO 2 and ZrO 2 are 3%, N
If b 2 O 5 and Ta 2 O 5 exceed 7%, they are likely to remain unmelted during glass melting, and it is necessary to raise the melting temperature, and as a result, it becomes difficult to stabilize Cu 2+ . Therefore Si
The composition range of O 2 , TiO 2 , and ZrO 2 is 0 to 3%, respectively.
The composition range of Nb 2 O 5 is limited to 0 to 5%, and the composition range of Ta 2 O 5 is limited to 0 to 7%. Si
The composition range of O 2 , TiO 2 , and ZrO 2 is 0 to 2%, respectively.
The composition range of Nb 2 O 5 is preferably 0 to 3%, and the composition range of Ta 2 O 5 is preferably 0 to 5%.
【００２９】Ｇａ2Ｏ3、ＧｅＯ2、ＷＯ3は少量の添加に
よって化学的耐久性を良化させる成分であるが、Ｇａ2
Ｏ3、ＧｅＯ2は３％、ＷＯ3は５％を上回ると結晶化傾
向が強まる。従ってＧａ2Ｏ3、ＧｅＯ2の組成範囲はそ
れぞれは０〜３％、ＷＯ3の組成範囲は０〜５％に限定
される。Ｇａ2Ｏ3、ＧｅＯ2の組成範囲はそれぞれは０
〜２％が好ましく、ＷＯ3の組成範囲は０〜３％が好ま
しい。Ga 2 O 3 , GeO 2 and WO 3 are components that improve the chemical durability by adding a small amount, but Ga 2
If O 3 and GeO 2 are more than 3% and WO 3 is more than 5%, the crystallization tendency becomes stronger. Therefore, the composition range of Ga 2 O 3 and GeO 2 is limited to 0 to 3%, and the composition range of WO 3 is limited to 0 to 5%. The composition range of Ga 2 O 3 and GeO 2 is 0 respectively.
˜2% is preferable, and the composition range of WO 3 is preferably 0 to 3%.
【００３０】上記したＬａ2Ｏ3、Ｙ2Ｏ3、Ｇｄ2Ｏ3、Ｂ
ｉ2Ｏ3、Ｉｎ2Ｏ3、Ｓｃ2Ｏ3、ＳｉＯ2、ＴｉＯ2、Ｚｒ
Ｏ2、Ｎｂ2Ｏ5、Ｔａ2Ｏ5、Ｇａ2Ｏ3、ＧｅＯ2、ＷＯ3
を以下、高原子価金属酸化物と総称するが、高原子価金
属酸化物の合量が１０％を上回ると、ガラスの熔解性が
悪化するだけでなく、結晶化傾向が強くなるので高原子
価金属酸化物の合量は０〜１０％とするのが望ましい。The above-mentioned La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and B
i 2 O 3 , In 2 O 3 , Sc 2 O 3 , SiO 2 , TiO 2 , Zr
O 2 , Nb 2 O 5 , Ta 2 O 5 , Ga 2 O 3 , GeO 2 , WO 3
Are collectively referred to as high valence metal oxides below. However, if the total content of high valence metal oxides exceeds 10%, not only the meltability of the glass deteriorates, but also the crystallization tendency becomes strong, so high atoms are contained. The total amount of valent metal oxides is preferably 0-10%.
【００３１】ＳｎＯはガラスの化学的耐久性を良化する
成分であるが、５％を上回ると透過率特性が悪化し、又
結晶化傾向が強まる。従ってＳｎＯの組成範囲は０〜５
％に限定され、好ましくは０〜３％である。SnO is a component that improves the chemical durability of glass, but if it exceeds 5%, the transmittance characteristics deteriorate and the crystallization tendency increases. Therefore, the composition range of SnO is 0-5.
%, And preferably 0 to 3%.
【００３２】Ｓｂ2Ｏ3はＣｕ2+を安定にし耐失透性を改
善する効果があるが、２５％を上回ると耐候性が悪化す
る。よってＳｂ2Ｏ3の組成範囲は０〜２５％に限定さ
れ、好ましくは０〜１５％である。Sb 2 O 3 has the effect of stabilizing Cu 2+ and improving the devitrification resistance, but if it exceeds 25%, the weather resistance deteriorates. Therefore, the composition range of Sb 2 O 3 is limited to 0 to 25%, preferably 0 to 15%.
【００３３】ＣｅＯ2は脱泡及びＣｕＯの酸化剤として
使用できるが、２％を超えると紫外部の透過特性を悪化
させる。従ってＣｅＯ2の組成範囲は０〜２％に限定さ
れ、好ましくは０〜１％である。CeO 2 can be used as a defoaming agent and an oxidant for CuO, but if it exceeds 2%, the ultraviolet transmission characteristics are deteriorated. Therefore, the composition range of CeO 2 is limited to 0 to 2%, preferably 0 to 1%.
【００３４】またＦは熔解温度を低下させＣｕ2+の安定
な着色を得るために有効な成分であるが、結晶化傾向を
強めず、熱膨張係数を高めない範囲は２０％までであ
る。従ってＦの組成範囲は０〜２０％に限定され、好ま
しくは０〜１５％である。なお、Ｆは酸化物の一部を弗
化物に置き換えることにより供給できる。Further, F is an effective component for lowering the melting temperature and obtaining stable coloring of Cu 2+ , but the range which does not strengthen the crystallization tendency and does not increase the thermal expansion coefficient is up to 20%. Therefore, the composition range of F is limited to 0 to 20%, preferably 0 to 15%. Note that F can be supplied by replacing a part of the oxide with a fluoride.
【００３５】上記の組成からなる本発明の近赤外吸収フ
ィルターガラスは、（ａ）４００〜６００ｎｍの光を高
透過させ、６００ｎｍ以上の光をシャープに吸収する、
（ｂ）熱膨張係数（α100 〜300 ）が小さく、加工中に
割れなどの問題が生じ難い、（ｃ）６５℃、９０％相対
湿度下において１０００時間保持したときの保持前後の
ヘーズ値の差が小さく、長期間使用するに十分な耐候性
を有する、などの特長を有する。The near-infrared absorption filter glass of the present invention having the above composition (a) highly transmits light of 400 to 600 nm and sharply absorbs light of 600 nm or more,
(B) The coefficient of thermal expansion (α 100 to 300 ) is small, and problems such as cracking are less likely to occur during processing. (C) The haze value before and after holding when held at 65 ° C. and 90% relative humidity for 1000 hours. It has features such as small difference and sufficient weather resistance for long-term use.
【００３６】[0036]
【実施例】以下本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００３７】実施例１〜１８ 表１〜３にガラス組成を示す実施例１〜１８のガラスは
次のようにして作製した。 Examples 1 to 18 Glasses of Examples 1 to 18 whose glass compositions are shown in Tables 1 to 3 were prepared as follows.
【００３８】ガラス成分の原料として、酸化物それ自
体、炭酸塩、硝酸塩、水酸化物、フッ化物、燐酸塩など
を使用した。例えば実施例３のガラスは、原料としてＨ
3ＰＯ4、Ａｌ（ＯＨ）3、ＫＮＯ3、ＢａＣＯ3、ＣａＣ
Ｏ3、ＺｎＯ、Ａｓ2Ｏ3、ＣｕＯを使用した。尚、原料
としてメタ燐酸アルミニウム、メタ燐酸亜鉛等の複合塩
の使用を妨げるものではない。また熱膨張係数を高めず
に２０％までのＦを添加することができるが、特にフッ
化物原料を特定するものではない。As the raw material of the glass component, oxide itself, carbonate, nitrate, hydroxide, fluoride, phosphate or the like was used. For example, the glass of Example 3 uses H as a raw material.
3 PO 4 , Al (OH) 3 , KNO 3 , BaCO 3 , CaC
O 3 , ZnO, As 2 O 3 and CuO were used. It should be noted that the use of composite salts such as aluminum metaphosphate and zinc metaphosphate as a raw material is not hindered. Further, up to 20% of F can be added without increasing the coefficient of thermal expansion, but it does not particularly specify the fluoride raw material.
【００３９】これらの原料を使用しバッチをよく混合し
た後、白金製坩堝で９００〜１２５０℃で溶融し、撹
拌、脱泡、均質化を行った後、余熱しておいた金型に鋳
込み、徐冷することにより、ブロック状の実施例１〜１
８のガラスを得た。得られた実施例１〜１８のガラス組
成を表１〜３に示す。After using these raw materials and mixing the batch well, the mixture was melted in a platinum crucible at 900 to 1250 ° C., stirred, defoamed and homogenized, and then cast into a preheated mold, By gradually cooling, the block-shaped Examples 1 to 1
A glass of 8 was obtained. The glass compositions of Examples 1 to 18 obtained are shown in Tables 1 to 3.
【００４０】得られた実施例１〜１８のガラスの透過率
曲線、熱膨張係数（α100 〜300 ）、液相温度（℃）お
よびヘーズ値の差（％）を下記の方法で求めた。The transmittance curves, coefficient of thermal expansion (α 100 to 300 ), liquidus temperature (° C.) and haze value difference (%) of the obtained glasses of Examples 1 to 18 were determined by the following methods.
【００４１】（１）透過率曲線 島津分光光度計ＵＶ３１０１−ＰＣを用いて測定した。(1) Transmittance curve Measured with a Shimadzu spectrophotometer UV3101-PC.
【００４２】（２）熱膨張係数（α100 〜300 ） 熱機械分析装置により１００〜３００℃における熱膨張
係数を測定した。(2) Thermal expansion coefficient (α 100 to 300 ) The thermal expansion coefficient at 100 to 300 ° C. was measured by a thermomechanical analyzer.
【００４３】（３）液相温度（℃） 温度傾斜炉において３０分間保持した後、顕微鏡により
結晶の有無を観察し求めた。(3) Liquidus temperature (° C.) After holding in a temperature gradient furnace for 30 minutes, the presence or absence of crystals was observed by a microscope to determine the temperature.
【００４４】（４）ヘーズ値の差（％） ヘーズ値の差（％）は本発明において、ガラスの耐候性
の指標として用いたものである。ガラスブロックから厚
さ１ｍｍに鏡面研磨したサンプルを作製し、加速試験条
件（６５℃−９０％相対湿度下に１０００時間保持）下
に置き、ヘーズメーター（ＪＩＳ規格：Ｋ６７１４に基
づく）により、処理前後のヘーズ値の差ΔＨ（％）を求
め、ガラス表面の劣化の程度を数値化した。(4) Difference in haze value (%) The difference in haze value (%) is used as an index of the weather resistance of glass in the present invention. A mirror-polished sample with a thickness of 1 mm was prepared from a glass block, placed under accelerated test conditions (held at 65 ° C.-90% relative humidity for 1000 hours), and then treated with a haze meter (based on JIS standard: K6714) before and after treatment. The difference ΔH (%) in the haze value was calculated and the degree of deterioration of the glass surface was quantified.
【００４５】ここでヘーズ値（Ｈ）は、次式により求め
られるものである。Here, the haze value (H) is obtained by the following equation.
【００４６】Ｈ＝Ｔｄ／Ｔｔ×１００（％） Ｔｔ：全光量透過率（％） Ｔｄ：拡散透過率（％） 透過率曲線を測定した結果、実施例１〜１８のガラス
は、いずれも４００〜６００ｎｍの光を高透過させ、６
００ｎｍ以上の光をシャープに吸収するので近赤外吸収
フィルターガラスとして好適であることが明らかとなっ
た。図１に実施例３および実施例４のガラスの透過率曲
線を代表例として示す。H = Td / Tt × 100 (%) Tt: Total light amount transmittance (%) Td: Diffuse transmittance (%) As a result of measuring transmittance curves, all the glasses of Examples 1 to 18 were 400%. Highly transmits light of ~ 600nm, 6
It became clear that it is suitable as a near-infrared absorption filter glass because it absorbs light of 00 nm or more sharply. FIG. 1 shows the transmittance curves of the glasses of Examples 3 and 4 as a representative example.
【００４７】また実施例１〜１８のガラスは表１〜３に
示すように熱膨張係数α100 〜300が１３０以下であ
り、ガラスの加工、研磨の際に起きるカン、割れなどの
問題が起りにくいことが明らかとなった。Further, the glass of Examples 1 to 18 has a coefficient of thermal expansion α 100 to 300 of 130 or less as shown in Tables 1 to 3, and problems such as cans and cracks occur during the processing and polishing of the glass. It turned out to be difficult.
【００４８】また実施例１〜１８のガラスは、表１〜３
に示すように液相温度が９００℃以下であり、安定に大
量生産可能な耐失透性を有することが明らかとなった。The glasses of Examples 1 to 18 are shown in Tables 1 to 3.
As shown in, the liquidus temperature was 900 ° C. or lower, and it was revealed that the liquid crystal composition has devitrification resistance capable of stable mass production.
【００４９】また実施例１〜１８のガラスは、表１〜３
に示すようにヘーズ値の差ΔＨ（％）が２．５％以下で
あり、極めて優れた耐候性を有し、通常のＶＴＲカメラ
等の使用条件下では、長期にわたり安定した性能が維持
されることが明らかとなった。The glasses of Examples 1 to 18 are shown in Tables 1 to 3.
As shown in Fig. 3, the difference in haze value ΔH (%) is 2.5% or less, which has extremely excellent weather resistance, and stable performance is maintained for a long period of time under normal use conditions such as a VTR camera. It became clear.
【００５０】[0050]
【表１】 [Table 1]
【００５１】[0051]
【表２】 [Table 2]
【００５２】[0052]
【表３】 [Table 3]
【００５３】比較例１〜３ 比較例１のガラスは、ガラス成分が本発明のガラス成分
に含まれるが、Ｐ2Ｏ5の量が５４．０％であり、本発明
のガラスにおけるＰ2Ｏ5の上限５０％を超えるガラスで
ある。[0053] glasses of Comparative Examples 1 to 3 Comparative Example 1, a glass component is contained in the glass component of the present invention, the amount of P 2 O 5 is the 54.0%, P 2 O in the glass of the present invention It is a glass with an upper limit of 5 exceeding 50%.
【００５４】比較例２のガラスは、ガラス成分が本発明
のガラス成分に含まれるが、アルカリ金属酸化物Ｒ2Ｏ
の量が２３．０％であり、本発明のガラスにおけるＲ2
Ｏの上限２０％を超えるガラスである。In the glass of Comparative Example 2, the glass component is contained in the glass component of the present invention, but the alkali metal oxide R 2 O is used.
The amount of R 2 in the glass of the present invention is 23.0%.
It is a glass in which the upper limit of O is 20%.
【００５５】比較例３のガラスは、特開平４−１０４９
８１号公報に実施例１として記載されている燐酸塩系ガ
ラスであり、Ｐ2Ｏ5の量が６０％を超え、比較的多量の
Ａｌ2Ｏ3を含有するガラスである。The glass of Comparative Example 3 is the glass of Japanese Patent Laid-Open No. 1049/1992.
This is the phosphate glass described as Example 1 in Japanese Patent Publication No. 81, in which the amount of P 2 O 5 exceeds 60% and the glass contains a relatively large amount of Al 2 O 3 .
【００５６】これら比較例１〜３のガラスの詳細な組成
は表４に示した。Table 4 shows the detailed compositions of the glasses of Comparative Examples 1 to 3.
【００５７】これら比較例のガラスのうち、比較例３の
ガラスの透過率曲線を図１に示す。図１より明らかなよ
うに比較例３のガラスでは、実施例３のものと５００ｎ
ｍと７００ｎｍの透過率を合せたとき、４００ｎｍ付近
の透過率が低く、また６５℃−９０％の相対湿度下で１
０００時間保持した時の耐候性テストでは、ヘーズ値が
９１．５％であり、長期間の使用に対する信頼性に問題
であることがわかる。すなわち、比較例３のガラスは、
透過率特性、耐候性の面で本発明のガラスより著しく劣
る。FIG. 1 shows the transmittance curve of the glass of Comparative Example 3 among the glasses of these Comparative Examples. As is clear from FIG. 1, the glass of Comparative Example 3 had a glass content of 500 n compared with that of Example 3.
When the transmittances of m and 700 nm are combined, the transmittance around 400 nm is low, and it is 1 at 65 ° C.-90% relative humidity.
In the weather resistance test after holding for 000 hours, the haze value is 91.5%, which shows that there is a problem in reliability for long-term use. That is, the glass of Comparative Example 3 was
It is significantly inferior to the glass of the present invention in terms of transmittance characteristics and weather resistance.
【００５８】比較例１および２のガラスの熱膨張係数
（α100 〜300 ）、液相温度（℃）およびヘーズ値の差
ΔＨ（％）を表４に示すが、表４より明らかなように、
加工性の指標になる低い熱膨張係数（α100 〜300 ）と
耐候性の指標になる低いヘーズ値の差ΔＨ（％）の両者
を満足するものは得られていない。すなわち比較例１の
ガラスはα100 〜300 が１１７と低く、加工性に優れて
いるが、ヘーズ値の差ΔＨが８５．０％で耐候性に著し
く劣る。また比較例２のガラスは、α100 〜300が１４
５、ヘーズ値の差ΔＨが９０．０％であるので、加工
性、耐候性ともに劣る。Table 4 shows the thermal expansion coefficient (α 100 to 300 ), the liquidus temperature (° C.) and the difference in haze value ΔH (%) of the glasses of Comparative Examples 1 and 2, which are clearly shown in Table 4. ,
There is no material that satisfies both the low coefficient of thermal expansion (α 100 to 300 ) that is an index of workability and the difference ΔH (%) of low haze value that is an index of weather resistance. That is, the glass of Comparative Example 1 has a low α 100 to 300 of 117 and is excellent in workability, but the difference in haze value ΔH is 85.0% and the weatherability is remarkably poor. Further, in the glass of Comparative Example 2, α 100 to 300 is 14
5. Since the difference ΔH in haze value is 90.0%, both workability and weather resistance are poor.
【００５９】[0059]
【表４】 [Table 4]
【００６０】[0060]
【発明の効果】以上に説明したように本発明の近赤外吸
収フィルターガラスは、従来用いられていた燐酸塩系ガ
ラスよりも紫外部に於いて優れた透過率特性を有し、ま
た容易に大量生産可能なガラスの安定性と加工性を有す
る。さらに充分な耐候性を有するため、カラーＶＴＲカ
メラ等の色補正フィルターとして長期間にわたり性能の
維持が可能である。INDUSTRIAL APPLICABILITY As described above, the near-infrared absorption filter glass of the present invention has excellent transmittance characteristics in the ultraviolet region as compared with the conventionally used phosphate-based glass, and easily It has the stability and workability of glass that can be mass-produced. Further, since it has sufficient weather resistance, it can maintain its performance as a color correction filter for a color VTR camera or the like for a long period of time.
【図１】実施例３および４ならびに比較例３のガラスの
透過率曲線図である。FIG. 1 is a transmittance curve diagram of glasses of Examples 3 and 4 and Comparative Example 3.
Claims (8)
ィルターガラス。Wherein P 2 O 5 37~49% Li 2 O 0~3% Na 2 O 0~8% K 2 O 0~17% Cs 2 O 0~17% R 2 O (R in% by weight 2 to 17% ZnO 25 to 45% MgO 0 to 5% CaO 0 to 5% SrO 0 to 5% BaO 0 to 8% R'O (R 'is an alkaline earth metal) 0. 5-10% CuO 0.2-10% is included, The near-infrared absorption filter glass of Claim 1 characterized by the above-mentioned.
吸収フィルターガラス。3. Pt 2 O 5 40-48% Li 2 O 0-3% Na 2 O 0-6% K 2 O 0-17% Cs 2 O 0-15% R 2 O (R is 2 to 17% ZnO 27 to 42% MgO 0 to 5% CaO 0 to 5% SrO 0 to 5% BaO 0 to 8% R'O (R 'is an alkaline earth metal) 0. 5-10% CuO 0.2-10% is contained, The near-infrared absorption filter glass of Claim 1 or 2 characterized by the above-mentioned.
含むことを特徴とする請求項１〜３のいずれか一項に記
載の近赤外吸収フィルターガラス。4. As 2 O 3 is contained in an amount of 0.05 to 5% by weight.
The near-infrared absorption filter glass according to claim 1, wherein the near-infrared absorption filter glass is included.
記載の近赤外吸収フィルターガラス。5. As an optional component, B 2 O 3 0-10% Al 2 O 3 0-5% PbO 0-25% La 2 O 3 0-3% Y 2 O 3 0-3% Gd in weight%. 2 O 3 0 to 3% Bi 2 O 3 0 to 5% In 2 O 3 0 to 7% Sc 2 O 3 0 to 5% SiO 2 0 to 3% TiO 2 0 to 3% ZrO 2 0 to 3% Nb 2 O 5 0 to 5% Ta 2 O 5 0 to 7% Ga 2 O 3 0 to 3% GeO 2 0 to 3% WO 3 0 to 5% SnO 0 to 5% Sb 2 O 3 0 to 25% CeO 2 0-2% F 0-20% is contained, The near-infrared absorption filter glass as described in any one of Claims 1-4.
５〜３％ である、請求項１〜５のいずれか一項に記載の近赤外吸
収フィルターガラス。6. Al 2 O 3 0.
The near infrared absorption filter glass according to any one of claims 1 to 5, which is 5 to 3%.
みを含み、その組成範囲が１．５〜１７％である、請求
項１〜６のいずれか一項に記載の近赤外吸収フィルター
ガラス。Includes K 2 O only as 7. alkali metal oxides R 2 O, the composition range is from 1.5 to 17%, a near-infrared absorption according to any one of claims 1 to 6 Filter glass.
-7／℃以下であり、６５℃、９０％相対湿度下において
１０００時間保持したときの保持前後のヘーズ値の差
（％）が２．５％以下である、請求項１〜７のいずれか
一項に記載の近赤外吸収フィルターガラス。8. The coefficient of thermal expansion α 100 to 300 is 130 × 10.
-7 / ° C or less, and the difference (%) in haze value before and after holding when held at 65 ° C and 90% relative humidity for 1000 hours is 2.5% or less. The near-infrared absorption filter glass according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19105596A JPH09100136A (en) | 1995-07-24 | 1996-07-19 | Near infrared absorbing filter glass |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-186886 | 1995-07-24 | ||
| JP18688695 | 1995-07-24 | ||
| JP19105596A JPH09100136A (en) | 1995-07-24 | 1996-07-19 | Near infrared absorbing filter glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09100136A true JPH09100136A (en) | 1997-04-15 |
Family
ID=26504035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19105596A Withdrawn JPH09100136A (en) | 1995-07-24 | 1996-07-19 | Near infrared absorbing filter glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09100136A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6225244B1 (en) | 1998-01-21 | 2001-05-01 | Hoya Corporation | Glass for near absorption filter and near infrared absorption filter to which the glass is applied |
| FR2843747A1 (en) | 2002-08-23 | 2004-02-27 | Schott Glas | LEAD FREE HEAVY FLINTS |
| JP2004137100A (en) * | 2002-10-16 | 2004-05-13 | Hoya Corp | Copper-containing glass, near-infrared absorbing element, and near-infrared absorbing filter |
| JP2005082458A (en) * | 2003-09-10 | 2005-03-31 | Minolta Co Ltd | Optical glass and optical element |
| JP2005514590A (en) * | 2001-12-19 | 2005-05-19 | スリーエム イノベイティブ プロパティズ カンパニー | Optical filter for manipulating the spectral output distribution in an accelerated weathering device. |
| JP2008001543A (en) * | 2006-06-21 | 2008-01-10 | Agc Techno Glass Co Ltd | Visibility correction filter glass and visibility correction filter |
| CN101643314A (en) * | 2008-08-06 | 2010-02-10 | 柯尼卡美能达精密光学株式会社 | Optical glass and optical element |
| JP2010208934A (en) * | 2009-03-06 | 2010-09-24 | Schott Ag | Optical glass |
| JP2011121792A (en) * | 2009-12-08 | 2011-06-23 | Asahi Glass Co Ltd | Near infrared ray cutting filter glass |
| JP2015089855A (en) * | 2013-11-05 | 2015-05-11 | 日本電気硝子株式会社 | Near-infrared absorbing glass |
| WO2016171255A1 (en) * | 2015-04-24 | 2016-10-27 | 旭硝子株式会社 | Near infrared cut-off filter glass |
| KR20170038662A (en) * | 2015-09-30 | 2017-04-07 | 호야 칸데오 옵트로닉스 가부시키가이샤 | Ultraviolet transmiting and visible-light absorbing glass and ultraviolet transmiting and visible-light absorbing filter |
-
1996
- 1996-07-19 JP JP19105596A patent/JPH09100136A/en not_active Withdrawn
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6225244B1 (en) | 1998-01-21 | 2001-05-01 | Hoya Corporation | Glass for near absorption filter and near infrared absorption filter to which the glass is applied |
| JP2005514590A (en) * | 2001-12-19 | 2005-05-19 | スリーエム イノベイティブ プロパティズ カンパニー | Optical filter for manipulating the spectral output distribution in an accelerated weathering device. |
| FR2843747A1 (en) | 2002-08-23 | 2004-02-27 | Schott Glas | LEAD FREE HEAVY FLINTS |
| JP2004137100A (en) * | 2002-10-16 | 2004-05-13 | Hoya Corp | Copper-containing glass, near-infrared absorbing element, and near-infrared absorbing filter |
| JP2005082458A (en) * | 2003-09-10 | 2005-03-31 | Minolta Co Ltd | Optical glass and optical element |
| JP2008001543A (en) * | 2006-06-21 | 2008-01-10 | Agc Techno Glass Co Ltd | Visibility correction filter glass and visibility correction filter |
| CN101643314A (en) * | 2008-08-06 | 2010-02-10 | 柯尼卡美能达精密光学株式会社 | Optical glass and optical element |
| JP2010208934A (en) * | 2009-03-06 | 2010-09-24 | Schott Ag | Optical glass |
| JP2011121792A (en) * | 2009-12-08 | 2011-06-23 | Asahi Glass Co Ltd | Near infrared ray cutting filter glass |
| JP2015089855A (en) * | 2013-11-05 | 2015-05-11 | 日本電気硝子株式会社 | Near-infrared absorbing glass |
| WO2016171255A1 (en) * | 2015-04-24 | 2016-10-27 | 旭硝子株式会社 | Near infrared cut-off filter glass |
| JPWO2016171255A1 (en) * | 2015-04-24 | 2018-02-15 | 旭硝子株式会社 | Near-infrared cut filter glass |
| US10252936B2 (en) | 2015-04-24 | 2019-04-09 | AGC Inc. | Near-infrared cut filter glass |
| KR20170038662A (en) * | 2015-09-30 | 2017-04-07 | 호야 칸데오 옵트로닉스 가부시키가이샤 | Ultraviolet transmiting and visible-light absorbing glass and ultraviolet transmiting and visible-light absorbing filter |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20031007 |