WO2017208679A1 - Method and device for manufacturing near infrared absorbing glass - Google Patents

Method and device for manufacturing near infrared absorbing glass Download PDF

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Publication number
WO2017208679A1
WO2017208679A1 PCT/JP2017/016236 JP2017016236W WO2017208679A1 WO 2017208679 A1 WO2017208679 A1 WO 2017208679A1 JP 2017016236 W JP2017016236 W JP 2017016236W WO 2017208679 A1 WO2017208679 A1 WO 2017208679A1
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Prior art keywords
glass
molten glass
infrared absorbing
holding
absorbing glass
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PCT/JP2017/016236
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French (fr)
Japanese (ja)
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永野雄太
此下聡子
中塚和人
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日本電気硝子株式会社
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Priority claimed from JP2016201518A external-priority patent/JP6799273B2/en
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to CN201780033055.4A priority Critical patent/CN109195926B/en
Publication of WO2017208679A1 publication Critical patent/WO2017208679A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • 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
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to a manufacturing method and manufacturing apparatus for near-infrared absorbing glass capable of selectively absorbing near-infrared rays.
  • near-infrared-absorbing glass is used for correcting the visibility of solid-state imaging devices such as CCDs (Charge Coupled Devices) and CMOSs (Complementary Metal Oxide Semiconductors) on camera parts in optical devices such as digital cameras and smartphones. Is used.
  • CCDs Charge Coupled Devices
  • CMOSs Complementary Metal Oxide Semiconductors
  • Cu-containing phosphate glass is generally used.
  • Near-infrared absorbing glass also requires chemical durability and weather resistance for practical use, and therefore various improvements in composition and manufacturing methods have been made.
  • an object of the present invention is to provide a method and an apparatus capable of easily producing near-infrared absorbing glass excellent in spectral characteristics.
  • the manufacturing method of the near-infrared absorbing glass of the present invention is a manufacturing method of near-infrared absorbing glass containing P and Cu. After the raw material is heated and melted at a melting temperature T 1 to form a molten glass, the melting temperature T 1 characterized by holding the molten glass at a low holding temperature T 2. In this way, even when copper ions are reduced to Cu + in the molten glass, Cu + is easily oxidized to Cu 2+ by holding the molten glass at a holding temperature lower than the melting temperature. . Therefore, since the ratio of Cu ⁇ 2+> in the copper ion contained in the near-infrared absorption glass obtained can be increased, it is possible to obtain excellent spectral characteristics.
  • T 1 -T 2 is preferably 100 to 600 ° C.
  • T 1 is preferably 900 to 1400 ° C.
  • T 2 is preferably 800 to 1100 ° C.
  • the area of the liquid surface of the molten glass when holding the molten glass at the holding temperature T 2 is S (mm 2 ), and the depth of the molten glass is D (mm).
  • S / D ⁇ 100 (mm) oxygen in the air is easily taken into the molten glass, and the molten glass is easily oxidized.
  • the amount of Cu + ions that absorb in the ultraviolet region is reduced by oxidation, and the light transmittance from the ultraviolet region to the visible region is increased, so that a glass having excellent light transmittance in the visible region can be easily obtained.
  • the method of manufacturing a near-infrared-absorbing glass of the present invention when holding the molten glass at the holding temperature T 2, it is preferred that bubbling oxygen into molten glass. If it does in this way, oxygen will be taken in in molten glass and it will become easy to oxidize molten glass. As a result, the amount of Cu + ions that absorb in the ultraviolet region is reduced by oxidation, and the light transmittance from the ultraviolet region to the visible region is increased, so that a glass having excellent light transmittance in the visible region can be easily obtained.
  • Apparatus for manufacturing a near-infrared absorbing glass holding tank for holding the molten bath to obtain a molten glass by heat dissolving raw materials at a melt temperatures T 1, the molten glass at the melting temperature T 1 of a lower holding temperature T 2 It is characterized by having.
  • a manufacturing apparatus provided with a melting tank and a holding tank in this manner, the raw material can be heated and melted and the molten glass can be kept at a low temperature, so that the production efficiency can be increased.
  • FIG. 4 is a graph showing light transmittance curves of an example sample a and a comparative example sample a in Experiment 1.
  • FIG. In Experiment 2 it is a graph which shows the relationship between the value of ratio S / D of the liquid surface area S and the depth D of molten glass, and the light transmittance in wavelength 500nm. It is a graph which shows the light transmittance curve of the sample n which did the oxygen bubbling in the experiment 3, and the sample b which did not oxygen bubbling.
  • the method of manufacturing the near-infrared-absorbing glass of the present invention is a method for manufacturing a near-infrared-absorbing glass comprising P and Cu, after the molten glass was heated and dissolved material in the melting temperatures T 1, the melting temperatures T 1 characterized by holding the molten glass at a low holding temperature T 2.
  • the melting temperature T 1 is preferably 900 to 1400 ° C., 1000 to 1300 ° C., particularly 1100 to 1250 ° C.
  • the melting temperature T 1 is too low, homogeneous glass is hardly obtained.
  • the melting temperature T 1 is too high, Cu ions are reduced and easily shifted from Cu 2+ to Cu + , making it difficult to obtain desired optical characteristics.
  • the holding temperature T 2 is preferably 800 to 1100 ° C., particularly preferably 850 to 1000 ° C.
  • the holding temperature T 2 is preferably 800 to 1100 ° C., particularly preferably 850 to 1000 ° C.
  • the holding time of the molten glass at the holding temperature T 2 is preferably 1 to 20 hours, particularly 3 to 18 hours. If the holding time is too short, Cu + is not sufficiently oxidized to Cu 2+ and it becomes difficult to obtain desired optical characteristics. On the other hand, if the holding time is too long, the glass component volatilizes and it becomes difficult to obtain a desired composition. As a result, there is a possibility of adversely affecting each characteristic such as weather resistance, devitrification resistance, and optical characteristics.
  • the difference T 1 -T 2 between the melting temperature T 1 and the holding temperature T 2 is preferably 100 to 600 ° C., 150 to 500 ° C., particularly 200 to 400 ° C. If T 1 -T 2 is too small, Cu + is not sufficiently oxidized to Cu 2+ and it becomes difficult to obtain desired optical characteristics. On the other hand, if T 1 -T 2 is too large, devitrification tends to occur during holding of the molten glass or during molding.
  • S / D is preferably 200 (mm) or more, 500 (mm) or more, and particularly preferably 800 (mm) or more.
  • the upper limit of S / D is not particularly limited, but is preferably 10000000 (mm) or less, 500,000 (mm) or less, and particularly preferably 100000 (mm) or less in consideration of restrictions on production facilities and productivity.
  • bubbling oxygen into molten glass when holding the molten glass at the holding temperature T 2. If it does in this way, as mentioned above, it will become easy to obtain the glass excellent in the light transmittance in a visible region.
  • the temperature of the molten glass using one melting tank may be changed as described above, but the molten glass was heated and dissolved material in the melting temperatures T 1 It is preferable to use a manufacturing apparatus having a melting tank for obtaining and a holding tank for holding the molten glass at a holding temperature T 2 lower than the melting temperature T 1 .
  • the production apparatus with the melting tank and the holding tank set at respective predetermined temperatures, the introduction of the raw material into the melting tank and the movement of the molten glass from the melting tank to the holding tank are appropriately performed. Since production can be performed continuously, production efficiency can be increased.
  • the molten glass held in the holding tank for a certain time is then formed into a desired shape.
  • a downdraw apparatus, a roll forming apparatus, or the like is used as the forming apparatus.
  • the molded glass is subjected to post-processing such as cutting and polishing as necessary to obtain a near-infrared absorbing glass.
  • the composition of the near-infrared absorbing glass in the present invention is not particularly limited as long as it contains P and Cu, but for example, by mass%, P 2 O 5 20-80%, Al 2 O 3 2-20%, CuO 0 1-20%, R 2 O 0-50% (where R is at least one selected from Li, Na and K), R′O 0-50% (where R ′ is Mg, Ca, Sr) And at least one selected from Ba).
  • R is at least one selected from Li, Na and K
  • R′O 0-50% where R ′ is Mg, Ca, Sr
  • Ba at least one selected from Ba
  • P 2 O 5 is an essential component for forming a glass skeleton.
  • the content of P 2 O 5 is preferably 20 to 80%, 35 to 75%, particularly 50 to 70%.
  • desired optical characteristics are difficult to obtain. Specifically, the near-infrared absorption characteristics are likely to deteriorate.
  • the weather resistance tends to lower.
  • Al 2 O 3 is a component that greatly improves the weather resistance.
  • the content of Al 2 O 3 is 2-20% 5 to 17% is preferably particularly 8-14%.
  • the content of Al 2 O 3 is too small, the effect is difficult to obtain.
  • the content of Al 2 O 3 is too large, there is a tendency that the melting temperature fusible reduced increases.
  • CuO is an essential component for absorbing near infrared rays.
  • the CuO content is preferably 0.1 to 20%, 0.3 to 15%, particularly preferably 0.4 to 13%.
  • the CuO content is preferably adjusted as appropriate depending on the plate thickness. Specifically, it is preferable that the CuO content is increased as the plate thickness is decreased (the CuO content is decreased as the plate thickness is increased).
  • R 2 O (where R is at least one selected from Li, Na, and K) is a component that lowers the melting temperature.
  • the content of R 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%. When the content of R 2 O is too large, it is difficult to vitrify.
  • a preferable range of each component of R 2 O is as follows.
  • the content of Na 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%.
  • the content of Li 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%.
  • the content of K 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%.
  • R′O (where R ′ is at least one selected from Mg, Ca, Sr, and Ba) is a component that improves the weather resistance and improves the meltability.
  • the content of R′O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%. If the content of R′O is too large, crystals due to the R′O component tend to precipitate during molding.
  • the preferable range of the content of each component of R′O is as follows.
  • MgO is a component that improves weather resistance.
  • the MgO content is preferably 0 to 15%, particularly preferably 0.4 to 7%. When there is too much content of MgO, it will become difficult to vitrify.
  • CaO is a component that improves the weather resistance like MgO.
  • the CaO content is preferably 0 to 15%, particularly preferably 0.4 to 7%. When there is too much content of CaO, it will become difficult to vitrify.
  • SrO is a component that improves the weather resistance as well as MgO.
  • the SrO content is preferably 0 to 12%, particularly preferably 0.3 to 5%. When there is too much content of SrO, it will become difficult to vitrify.
  • BaO is a component that increases the stability of vitrification and improves the weather resistance. Especially when less is P 2 O 5, to easily enjoy the effect of vitrification stability by BaO.
  • the content of BaO is preferably 0 to 30%, 5 to 30%, 7 to 25%, particularly 7.2 to 23%. When there is too much content of BaO, the crystal
  • the near infrared absorbing glass may contain the following components.
  • ZnO is a component that improves the stability and weather resistance of vitrification.
  • the content of ZnO is preferably 0 to 13%, 0.1 to 12%, particularly 1 to 10%.
  • a meltability will fall and a melting temperature will become high, and it will become difficult to obtain a desired optical characteristic as a result.
  • crystals due to the ZnO component are likely to precipitate.
  • the amount of P 2 O 5 is small, it is easy to enjoy the effect of vitrification stability due to ZnO.
  • Nb 2 O 5 and Ta 2 O 5 are components that enhance the weather resistance.
  • the content of each component of Nb 2 O 5 and Ta 2 O 5 is preferably 0 to 20%, 0.1 to 20%, 1 to 18%, particularly 2 to 15%. When there is too much content of these components, melting temperature will become high and it will become difficult to obtain a desired optical characteristic.
  • the total amount of Nb 2 O 5 and Ta 2 O 5 is preferably 0 to 20%, 0.1 to 20%, 1 to 18%, particularly preferably 2 to 15%.
  • GeO 2 is a component that enhances weather resistance.
  • the GeO 2 content is preferably 0 to 20%, 0.1 to 20%, 0.3 to 17%, particularly preferably 0.4 to 15%.
  • the content of GeO 2 is too small, the effect is difficult to obtain.
  • the content of GeO 2 is too large, the melting temperature becomes high and it becomes difficult to obtain desired optical characteristics.
  • SiO 2 is a component that reinforces the glass skeleton. Moreover, there exists an effect which improves a weather resistance.
  • the content of SiO 2 is preferably 0 to 10%, 0.1 to 8%, particularly 1 to 6%. When the content of SiO 2 is too large, rather weather resistance tends to lower. Also, vitrification tends to be unstable.
  • B 2 O 3, Y 2 O 3, La 2 O 3, may be a CeO 2, Sb 2 O 3 or the like is contained in a range that does not impair the effects of the present invention.
  • the content of these components is preferably 0 to 3%, particularly preferably 0 to 2%.
  • fluorine is preferably not contained because it is an environmentally hazardous substance.
  • the liquid phase temperature of the near infrared ray absorbing glass is preferably 770 ° C. or lower, particularly preferably 750 ° C. or lower. If the liquidus temperature is too high, devitrification tends to occur in the manufacturing process (particularly during molding).
  • the near-infrared absorbing glass obtained by the above method can achieve both high light transmittance in the visible range and excellent light absorption characteristics in the near-infrared range.
  • the light transmittance at a wavelength of 550 nm is preferably 79% or more, particularly preferably 80% or more.
  • the light transmittance at a wavelength of 700 nm is preferably 13% or less, particularly preferably 11% or less, and the light transmittance at a wavelength of 1200 nm is preferably 25% or less, particularly preferably 20% or less.
  • Near-infrared absorbing glass is usually used in the form of a plate.
  • the thickness is preferably 0.01 to 1.2 mm, particularly 0.05 to 1.2 mm. If the thickness is too small, the mechanical strength tends to be inferior. On the other hand, if the thickness is too large, it is difficult to reduce the thickness of the optical device.
  • both surfaces were mirror-polished so that it might be set to 0.5 mm thickness, and the sample a (near-infrared absorption glass) was obtained.
  • the light transmittance of the obtained sample was measured in the wavelength range of 300 to 1300 nm using a spectrophotometer (UV-3100PC manufactured by Shimadzu Corporation). The results are shown in FIG.
  • the area of the liquid surface of the molten glass was 4416 mm 2 and the depth was 4.5 mm.
  • Sample A was prepared in the same manner as described above except that the step of holding the molten glass at 900 ° C. was not performed. About the obtained sample, the light transmittance was measured like the above. The results are shown in FIG.
  • the sample a of the example has a higher light transmittance in the visible region than the sample A of the comparative example, and sharply cuts near-infrared light.
  • Example 2 Samples b to m were prepared in the same manner as in Experiment 1 except that the liquid surface area and depth of the molten glass were changed as shown in Table 1, and the light transmittance at a wavelength of 500 nm was measured. The results are shown in Table 1 and FIG. FIG. 2 also shows a linear approximation curve together with the data plot. The area of the liquid surface of the molten glass was adjusted by appropriately changing the size (diameter) of the platinum crucible to be used.
  • Example 3 Except that the liquid surface area of the molten glass was 4416 mm 2 , the depth was 17 mm, and oxygen was bubbled into the molten glass when the molten glass was held at 900 ° C. Sample n was prepared. For comparison, a sample B that was not subjected to oxygen bubbling was also prepared. The light transmittance of these samples was measured in the wavelength range of 300 to 1300 nm. The results are shown in FIG.

Abstract

Provided is a method and device for easily manufacturing a near infrared absorbing glass that has excellent spectral characteristics. The method for manufacturing near infrared absorbing glass that contains P and Cu is characterized by heating and melting a starting material at a melting temperature T1 to produce molten glass, and then keeping the molten glass at a holding temperature T2 which is lower than the melting temperature T1.

Description

近赤外線吸収ガラスの製造方法及び製造装置Manufacturing method and manufacturing apparatus of near-infrared absorbing glass
　本発明は、近赤外線を選択的に吸収することが可能な近赤外線吸収ガラスの製造方法及び製造装置に関するものである。 The present invention relates to a manufacturing method and manufacturing apparatus for near-infrared absorbing glass capable of selectively absorbing near-infrared rays.
　一般に、デジタルカメラやスマートフォン等の光学デバイス内のカメラ部分には、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補性金属酸化膜半導体）等の固体撮像素子の視感度補正を目的として、近赤外線吸収ガラスが用いられている。近赤外線吸収ガラスとして必要な分光特性を満足するために、Ｃｕ含有リン酸ガラスが一般に用いられている。近赤外線吸収ガラスには、実用上、化学的耐久性や耐候性も要求されるため、組成及び製造方法の改良が種々行われてきた。 In general, near-infrared-absorbing glass is used for correcting the visibility of solid-state imaging devices such as CCDs (Charge Coupled Devices) and CMOSs (Complementary Metal Oxide Semiconductors) on camera parts in optical devices such as digital cameras and smartphones. Is used. In order to satisfy the spectral characteristics necessary for near infrared absorbing glass, Cu-containing phosphate glass is generally used. Near-infrared absorbing glass also requires chemical durability and weather resistance for practical use, and therefore various improvements in composition and manufacturing methods have been made.
　リン酸ガラスの化学的耐久性や耐候性を向上させるため、ガラス骨格を補強するＳｉＯ２やＡｌ２Ｏ３を含有させることが提案されている（例えば特許文献１参照）。しかしながら、その場合、溶融性が低下して溶融温度が上昇する傾向がある。溶融温度が上昇すると、近赤外域に吸収を示すＣｕ２＋イオンが還元され、紫外域に吸収を示すＣｕ＋イオンが生成し、紫外～可視域の光透過率が低下しやすくなるため、所望の光学特性が得にくくなる。 In order to improve the chemical durability and weather resistance of phosphate glass, it has been proposed to contain SiO 2 or Al 2 O 3 that reinforces the glass skeleton (see, for example, Patent Document 1). However, in that case, the meltability tends to decrease and the melting temperature tends to increase. As the melting temperature rises, Cu 2+ ions that absorb in the near infrared region are reduced, Cu + ions that absorb in the ultraviolet region are generated, and the light transmittance in the ultraviolet to visible region tends to decrease. Optical properties are difficult to obtain.
　そこで、銅の酸化状態を維持するために、原料に酸化剤を添加する方法が提案されている。 Therefore, in order to maintain the oxidation state of copper, a method of adding an oxidizing agent to the raw material has been proposed.
特開２０１１－１２１７９２号JP2011-121792A
　しかしながら、酸化剤の添加は、それ自身が分光特性に悪影響を及ぼす可能性がある。 However, the addition of an oxidant itself may adversely affect the spectral characteristics.
　以上に鑑み、本発明は、分光特性に優れた近赤外線吸収ガラスを容易に製造することが可能な方法及び装置を提供することを目的とする。 In view of the above, an object of the present invention is to provide a method and an apparatus capable of easily producing near-infrared absorbing glass excellent in spectral characteristics.
　本発明の近赤外線吸収ガラスの製造方法は、Ｐ及びＣｕを含む近赤外線吸収ガラスの製造方法であって、原料を溶融温度Ｔ１で加熱溶解して溶融ガラスにした後、溶融温度Ｔ１より低い保持温度Ｔ２で溶融ガラスを保持することを特徴とする。このようにすれば、溶融ガラス中において銅イオンがＣｕ＋に還元された場合であっても、溶融温度より低い保持温度で溶融ガラスを保持することで、Ｃｕ＋がＣｕ２＋に酸化されやすくなる。そのため、得られる近赤外線吸収ガラスに含まれる銅イオンにおけるＣｕ２＋の割合を高めることができるため、優れた分光特性を得ることが可能となる。 The manufacturing method of the near-infrared absorbing glass of the present invention is a manufacturing method of near-infrared absorbing glass containing P and Cu. After the raw material is heated and melted at a melting temperature T 1 to form a molten glass, the melting temperature T 1 characterized by holding the molten glass at a low holding temperature T 2. In this way, even when copper ions are reduced to Cu + in the molten glass, Cu + is easily oxidized to Cu 2+ by holding the molten glass at a holding temperature lower than the melting temperature. . Therefore, since the ratio of Cu <2+> in the copper ion contained in the near-infrared absorption glass obtained can be increased, it is possible to obtain excellent spectral characteristics.
　本発明の近赤外線吸収ガラスの製造方法において、Ｔ１－Ｔ２が１００～６００℃であることが好ましい。 In the method for producing a near-infrared absorbing glass of the present invention, T 1 -T 2 is preferably 100 to 600 ° C.
　本発明の近赤外線吸収ガラスの製造方法において、Ｔ１が９００～１４００℃であることが好ましい。 In the method for producing near-infrared absorbing glass of the present invention, T 1 is preferably 900 to 1400 ° C.
　本発明の近赤外線吸収ガラスの製造方法において、Ｔ２が８００～１１００℃であることが好ましい。 In the method for producing near-infrared absorbing glass of the present invention, T 2 is preferably 800 to 1100 ° C.
　本発明の近赤外線吸収ガラスの製造方法において、近赤外線吸収ガラスが、質量％で、Ｐ２Ｏ５　２０～８０％、Ａｌ２Ｏ３　２～２０％、ＣｕＯ　０．１～２０％、Ｒ２Ｏ　０～５０％（ただし、ＲはＬｉ、Ｎａ及びＫから選択される少なくとも１種）、Ｒ’Ｏ　０～５０％（ただし、Ｒ’はＭｇ、Ｃａ、Ｓｒ及びＢａから選択される少なくとも１種）を含有することが好ましい。 The method of manufacturing a near-infrared-absorbing glass of the present invention, near-infrared absorbing glass, in mass%, P 2 O 5 20 ~ 80%, Al 2 O 3 2 ~ 20%, CuO 0.1 ~ 20%, R 2 O 0-50% (where R is at least one selected from Li, Na and K), R′O 0-50% (where R ′ is at least one selected from Mg, Ca, Sr and Ba) It is preferable to contain a seed.
　本発明の近赤外線吸収ガラスの製造方法において、保持温度Ｔ２で溶融ガラスを保持する際の溶融ガラスの液面の面積をＳ（ｍｍ２）、溶融ガラスの深さをＤ（ｍｍ）とした場合、Ｓ／Ｄ≧１００（ｍｍ）の関係を満たすことが好ましい。このようにすれば、溶融ガラス中に空気中の酸素が取り込まれやすくなり、溶融ガラスが酸化されやすくなる。その結果、紫外域に吸収を示すＣｕ＋イオンの量が酸化により少なくなり紫外～可視域にわたる光透過率が上昇するため、可視域における光透過率に優れたガラスが得られやすくなる。 In the manufacturing method of the near-infrared absorbing glass of the present invention, the area of the liquid surface of the molten glass when holding the molten glass at the holding temperature T 2 is S (mm 2 ), and the depth of the molten glass is D (mm). In this case, it is preferable to satisfy the relationship of S / D ≧ 100 (mm). In this way, oxygen in the air is easily taken into the molten glass, and the molten glass is easily oxidized. As a result, the amount of Cu + ions that absorb in the ultraviolet region is reduced by oxidation, and the light transmittance from the ultraviolet region to the visible region is increased, so that a glass having excellent light transmittance in the visible region can be easily obtained.
　本発明の近赤外線吸収ガラスの製造方法において、保持温度Ｔ２で溶融ガラスを保持する際に、溶融ガラス中に酸素をバブリングすることが好ましい。このようにすれば、溶融ガラス中に酸素が取り込まれ、溶融ガラスが酸化されやすくなる。その結果、紫外域に吸収を示すＣｕ＋イオンの量が酸化により少なくなり紫外～可視域にわたる光透過率が上昇するため、可視域における光透過率に優れたガラスが得られやすくなる。 The method of manufacturing a near-infrared-absorbing glass of the present invention, when holding the molten glass at the holding temperature T 2, it is preferred that bubbling oxygen into molten glass. If it does in this way, oxygen will be taken in in molten glass and it will become easy to oxidize molten glass. As a result, the amount of Cu + ions that absorb in the ultraviolet region is reduced by oxidation, and the light transmittance from the ultraviolet region to the visible region is increased, so that a glass having excellent light transmittance in the visible region can be easily obtained.
　近赤外線吸収ガラスの製造装置は、原料を溶融温度Ｔ１で加熱溶解して溶融ガラスを得るための溶融槽と、溶融温度Ｔ１より低い保持温度Ｔ２で溶融ガラスを保持するための保持槽と、を有することを特徴とする。このように溶融槽と保持槽を設けた製造装置を用いることにより、原料の加熱溶解と、溶融ガラスの低温保持を連続的に行うことができるため、生産効率を高めることができる。 Apparatus for manufacturing a near-infrared absorbing glass, holding tank for holding the molten bath to obtain a molten glass by heat dissolving raw materials at a melt temperatures T 1, the molten glass at the melting temperature T 1 of a lower holding temperature T 2 It is characterized by having. By using a manufacturing apparatus provided with a melting tank and a holding tank in this manner, the raw material can be heated and melted and the molten glass can be kept at a low temperature, so that the production efficiency can be increased.
　本発明の製造方法及び製造装置によれば、分光特性に優れた近赤外線吸収ガラスを容易に製造することが可能となる。 According to the production method and production apparatus of the present invention, it is possible to easily produce near-infrared absorbing glass excellent in spectral characteristics.
実験１における実施例の試料ａ及び比較例の試料イの光透過率曲線を示すグラフである。4 is a graph showing light transmittance curves of an example sample a and a comparative example sample a in Experiment 1. FIG. 実験２において、溶融ガラスの液面の面積Ｓと深さＤの比Ｓ／Ｄの値と、波長５００ｎｍにおける光透過率の関係を示すグラフである。In Experiment 2, it is a graph which shows the relationship between the value of ratio S / D of the liquid surface area S and the depth D of molten glass, and the light transmittance in wavelength 500nm. 実験３における酸素バブリングした試料ｎ及び酸素バブリングしなかった試料ロの光透過率曲線を示すグラフである。It is a graph which shows the light transmittance curve of the sample n which did the oxygen bubbling in the experiment 3, and the sample b which did not oxygen bubbling.
　本発明の近赤外線吸収ガラスの製造方法は、Ｐ及びＣｕを含む近赤外線吸収ガラスの製造方法であって、原料を溶融温度Ｔ１で加熱溶解して溶融ガラスにした後、溶融温度Ｔ１より低い保持温度Ｔ２で溶融ガラスを保持することを特徴とする。 The method of manufacturing the near-infrared-absorbing glass of the present invention is a method for manufacturing a near-infrared-absorbing glass comprising P and Cu, after the molten glass was heated and dissolved material in the melting temperatures T 1, the melting temperatures T 1 characterized by holding the molten glass at a low holding temperature T 2.
　溶融温度Ｔ１は９００～１４００℃、１０００～１３００℃、特に１１００～１２５０℃であることが好ましい。溶融温度Ｔ１が低すぎると、均質なガラスが得にくくなる。一方、溶融温度Ｔ１が高すぎると、Ｃｕイオンが還元されてＣｕ２＋からＣｕ＋にシフトしやすくなるため、所望の光学特性が得にくくなる。 The melting temperature T 1 is preferably 900 to 1400 ° C., 1000 to 1300 ° C., particularly 1100 to 1250 ° C. When the melting temperature T 1 is too low, homogeneous glass is hardly obtained. On the other hand, if the melting temperature T 1 is too high, Cu ions are reduced and easily shifted from Cu 2+ to Cu + , making it difficult to obtain desired optical characteristics.
　保持温度Ｔ２は８００～１１００℃、特に８５０～１０００℃であることが好ましい。保持温度Ｔ２が低すぎると、溶融ガラス保持中あるいは成形時に失透が発生しやすくなる。一方、保持温度Ｔ２が高すぎると、Ｃｕ＋がＣｕ２＋に十分に酸化されず、所望の光学特性が得にくくなる。なお、溶融ガラスの保持温度Ｔ２での保持時間は１～２０時間、特に３～１８時間であることが好ましい。保持時間が短すぎると、Ｃｕ＋がＣｕ２＋に十分に酸化されず、所望の光学特性が得にくくなる。一方、保持時間が長すぎると、ガラス成分が揮発して所望の組成が得られにくくなる。その結果、耐候性、耐失透性、光学特性等の各特性に悪影響を及ぼすおそれがある。 The holding temperature T 2 is preferably 800 to 1100 ° C., particularly preferably 850 to 1000 ° C. When the holding temperature T 2 is too low, devitrification is likely to occur during the molten glass holding or shaping. On the other hand, if the holding temperature T 2 is too high, Cu + is not sufficiently oxidized to Cu 2+ and it becomes difficult to obtain desired optical characteristics. The holding time of the molten glass at the holding temperature T 2 is preferably 1 to 20 hours, particularly 3 to 18 hours. If the holding time is too short, Cu + is not sufficiently oxidized to Cu 2+ and it becomes difficult to obtain desired optical characteristics. On the other hand, if the holding time is too long, the glass component volatilizes and it becomes difficult to obtain a desired composition. As a result, there is a possibility of adversely affecting each characteristic such as weather resistance, devitrification resistance, and optical characteristics.
　なお、溶融温度Ｔ１と保持温度Ｔ２の差Ｔ１－Ｔ２は１００～６００℃、１５０～５００℃、特に２００～４００℃であることが好ましい。Ｔ１－Ｔ２が小さすぎると、Ｃｕ＋がＣｕ２＋に十分に酸化されず、所望の光学特性が得にくくなる。一方、Ｔ１－Ｔ２が大きすぎると、溶融ガラス保持中あるいは成形時に失透が発生しやすくなる。 The difference T 1 -T 2 between the melting temperature T 1 and the holding temperature T 2 is preferably 100 to 600 ° C., 150 to 500 ° C., particularly 200 to 400 ° C. If T 1 -T 2 is too small, Cu + is not sufficiently oxidized to Cu 2+ and it becomes difficult to obtain desired optical characteristics. On the other hand, if T 1 -T 2 is too large, devitrification tends to occur during holding of the molten glass or during molding.
　なお、保持温度Ｔ２で溶融ガラスを保持する際の溶融ガラスの液面の面積をＳ（ｍｍ２）、溶融ガラスの深さをＤ（ｍｍ）とした場合、Ｓ／Ｄ≧１００（ｍｍ）の関係を満たすことが好ましい。このようにすれば、既述の通り、可視域における光透過率に優れたガラスが得られやすくなる。Ｓ／Ｄは２００（ｍｍ）以上、５００（ｍｍ）以上、特に８００（ｍｍ）以上であることが好ましい。Ｓ／Ｄの上限は特に限定されないが、製造設備の制約や生産性等を考慮して、１０００００００（ｍｍ）以下、５０００００（ｍｍ）以下、特に１０００００（ｍｍ）以下であることが好ましい。 In addition, when the area of the liquid surface of the molten glass when holding the molten glass at the holding temperature T 2 is S (mm 2 ) and the depth of the molten glass is D (mm), S / D ≧ 100 (mm) It is preferable to satisfy the relationship. If it does in this way, as mentioned above, it will become easy to obtain the glass excellent in the light transmittance in a visible region. S / D is preferably 200 (mm) or more, 500 (mm) or more, and particularly preferably 800 (mm) or more. The upper limit of S / D is not particularly limited, but is preferably 10000000 (mm) or less, 500,000 (mm) or less, and particularly preferably 100000 (mm) or less in consideration of restrictions on production facilities and productivity.
　また、保持温度Ｔ２で溶融ガラスを保持する際に溶融ガラス中に酸素をバブリングすることが好ましい。このようにすれば、既述の通り、可視域における光透過率に優れたガラスが得られやすくなる。 Further, it is preferred that bubbling oxygen into molten glass when holding the molten glass at the holding temperature T 2. If it does in this way, as mentioned above, it will become easy to obtain the glass excellent in the light transmittance in a visible region.
　本発明の方法で近赤外線吸収ガラスを製造する場合、１つの溶融槽を用いて溶融ガラスの温度を上記の通り変化させてもよいが、原料を溶融温度Ｔ１で加熱溶解して溶融ガラスを得るための溶融槽と、溶融温度Ｔ１より低い保持温度Ｔ２で溶融ガラスを保持するための保持槽と、を有する製造装置を用いることが好ましい。当該製造装置を用いれば、溶融槽と保持槽を各々所定温度に設定した状態で、溶融槽への原料の導入と、溶融槽から保持槽への溶融ガラスの移動を適宜行うことにより、ガラスの生産を連続的に行うことができるため、生産効率を高めることができる。保持槽で一定時間保持した溶融ガラスは、その後所望の形状に成形される。成形装置としてはダウンドロー装置やロール成形装置等が使用される。成形後のガラスは必要に応じて切断や研磨等の後加工を経て近赤外線吸収ガラスが得られる。 When producing a near-infrared absorbing glass by the method of the present invention, the temperature of the molten glass using one melting tank may be changed as described above, but the molten glass was heated and dissolved material in the melting temperatures T 1 It is preferable to use a manufacturing apparatus having a melting tank for obtaining and a holding tank for holding the molten glass at a holding temperature T 2 lower than the melting temperature T 1 . By using the production apparatus, with the melting tank and the holding tank set at respective predetermined temperatures, the introduction of the raw material into the melting tank and the movement of the molten glass from the melting tank to the holding tank are appropriately performed. Since production can be performed continuously, production efficiency can be increased. The molten glass held in the holding tank for a certain time is then formed into a desired shape. As the forming apparatus, a downdraw apparatus, a roll forming apparatus, or the like is used. The molded glass is subjected to post-processing such as cutting and polishing as necessary to obtain a near-infrared absorbing glass.
　本発明における近赤外線吸収ガラスの組成は、Ｐ及びＣｕを含むものであれば特に限定されないが、例えば質量％で、Ｐ２Ｏ５　２０～８０％、Ａｌ２Ｏ３　２～２０％、ＣｕＯ　０．１～２０％、Ｒ２Ｏ　０～５０％（ただし、ＲはＬｉ、Ｎａ及びＫから選択される少なくとも１種）、Ｒ’Ｏ　０～５０％（ただし、Ｒ’はＭｇ、Ｃａ、Ｓｒ及びＢａから選択される少なくとも１種）を含有するリン酸塩系ガラスが挙げられる。ガラス組成をこのように規制した理由を以下に説明する。 The composition of the near-infrared absorbing glass in the present invention is not particularly limited as long as it contains P and Cu, but for example, by mass%, P 2 O 5 20-80%, Al 2 O 3 2-20%, CuO 0 1-20%, R 2 O 0-50% (where R is at least one selected from Li, Na and K), R′O 0-50% (where R ′ is Mg, Ca, Sr) And at least one selected from Ba). The reason why the glass composition is regulated in this way will be described below.
　Ｐ２Ｏ５はガラス骨格を形成するために欠かせない成分である。Ｐ２Ｏ５の含有量は２０～８０％、３５～７５％、特に５０～７０％であることが好ましい。Ｐ２Ｏ５の含有量が少なすぎると、ガラス化しにくくなったり、所望の光学特性が得にくくなる。具体的には、近赤外線吸収特性が低下しやすくなる。一方、Ｐ２Ｏ５の含有量が多すぎると、耐候性が低下しやすくなる。 P 2 O 5 is an essential component for forming a glass skeleton. The content of P 2 O 5 is preferably 20 to 80%, 35 to 75%, particularly 50 to 70%. When the content of P 2 O 5 is too small, or not easily be vitrified, desired optical characteristics are difficult to obtain. Specifically, the near-infrared absorption characteristics are likely to deteriorate. On the other hand, when the content of P 2 O 5 is too large, the weather resistance tends to lower.
　Ａｌ２Ｏ３は耐候性を大幅に向上させる成分である。Ａｌ２Ｏ３の含有量は２～２０％、５～１７％、特に８～１４％であることが好ましい。Ａｌ２Ｏ３の含有量が少なすぎると、上記効果が得にくくなる。一方、Ａｌ２Ｏ３の含有量が多すぎると、溶融性が低下して溶融温度が上昇する傾向がある。 Al 2 O 3 is a component that greatly improves the weather resistance. The content of Al 2 O 3 is 2-20% 5 to 17% is preferably particularly 8-14%. When the content of Al 2 O 3 is too small, the effect is difficult to obtain. On the other hand, when the content of Al 2 O 3 is too large, there is a tendency that the melting temperature fusible reduced increases.
　ＣｕＯは近赤外線を吸収するための必須成分である。ＣｕＯの含有量は０．１～２０％、０．３～１５％、特に０．４～１３％であることが好ましい。ＣｕＯの含有量が少なすぎると、所望の近赤外線吸収特性が得にくくなる。一方、ＣｕＯの含有量が多すぎると、紫外～可視域の光透過率が低下しやすくなる。またガラス化しにくくなる。なお、所望の光学特性を得るため、ＣｕＯの含有量は板厚によって適宜調整することが好ましい。具体的には、板厚が小さいほどＣｕＯ含有量を多く（板厚が大きいほどＣｕＯ含有量を少なく）することが好ましい。 CuO is an essential component for absorbing near infrared rays. The CuO content is preferably 0.1 to 20%, 0.3 to 15%, particularly preferably 0.4 to 13%. When there is too little content of CuO, it will become difficult to obtain a desired near-infrared absorption characteristic. On the other hand, if the CuO content is too large, the light transmittance in the ultraviolet to visible range tends to decrease. Moreover, it becomes difficult to vitrify. In order to obtain desired optical characteristics, the CuO content is preferably adjusted as appropriate depending on the plate thickness. Specifically, it is preferable that the CuO content is increased as the plate thickness is decreased (the CuO content is decreased as the plate thickness is increased).
　Ｒ２Ｏ（ただし、ＲはＬｉ、Ｎａ及びＫから選択される少なくとも１種）は溶融温度を低下させる成分である。Ｒ２Ｏの含有量は０～５０％、３～３０％、特に５～２０％であることが好ましい。Ｒ２Ｏの含有量が多すぎると、ガラス化しにくくなる。 R 2 O (where R is at least one selected from Li, Na, and K) is a component that lowers the melting temperature. The content of R 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%. When the content of R 2 O is too large, it is difficult to vitrify.
　なお、Ｒ２Ｏの各成分の好ましい範囲は以下の通りである。Ｎａ２Ｏの含有量は０～５０％、３～３０％、特に５～２０％であることが好ましい。Ｌｉ２Ｏの含有量は０～５０％、３～３０％、特に５～２０％であることが好ましい。Ｋ２Ｏの含有量は０～５０％、３～３０％、特に５～２０％であることが好ましい。 A preferable range of each component of R 2 O is as follows. The content of Na 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%. The content of Li 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%. The content of K 2 O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%.
　Ｒ’Ｏ（ただし、Ｒ’はＭｇ、Ｃａ、Ｓｒ及びＢａから選択される少なくとも１種）は耐候性を改善するとともに、溶融性を向上させる成分である。Ｒ’Ｏの含有量は０～５０％、３～３０％、特に５～２０％であることが好ましい。Ｒ’Ｏの含有量が多すぎると、成形時にＲ’Ｏ成分起因の結晶が析出しやすくなる。 R′O (where R ′ is at least one selected from Mg, Ca, Sr, and Ba) is a component that improves the weather resistance and improves the meltability. The content of R′O is preferably 0 to 50%, 3 to 30%, particularly 5 to 20%. If the content of R′O is too large, crystals due to the R′O component tend to precipitate during molding.
　なお、Ｒ’Ｏの各成分の含有量の好ましい範囲は以下の通りである。 In addition, the preferable range of the content of each component of R′O is as follows.
　ＭｇＯは耐候性を改善する成分である。ＭｇＯの含有量は０～１５％、特に０．４～７％であることが好ましい。ＭｇＯの含有量が多すぎると、ガラス化しにくくなる。 MgO is a component that improves weather resistance. The MgO content is preferably 0 to 15%, particularly preferably 0.4 to 7%. When there is too much content of MgO, it will become difficult to vitrify.
　ＣａＯはＭｇＯと同様に耐候性を改善する成分である。ＣａＯの含有量は０～１５％、特に０．４～７％であることが好ましい。ＣａＯの含有量が多すぎると、ガラス化しにくくなる。 CaO is a component that improves the weather resistance like MgO. The CaO content is preferably 0 to 15%, particularly preferably 0.4 to 7%. When there is too much content of CaO, it will become difficult to vitrify.
　ＳｒＯもＭｇＯと同様に耐候性を改善する成分である。ＳｒＯの含有量は０～１２％、特に０．３～５％であることが好ましい。ＳｒＯの含有量が多すぎると、ガラス化しにくくなる。 SrO is a component that improves the weather resistance as well as MgO. The SrO content is preferably 0 to 12%, particularly preferably 0.3 to 5%. When there is too much content of SrO, it will become difficult to vitrify.
　ＢａＯはガラス化の安定性を高めるとともに、耐候性を向上させる成分である。特にＰ２Ｏ５が少ない場合に、ＢａＯによるガラス化安定性の効果を享受しやすい。ＢａＯの含有量は０～３０％、５～３０％、７～２５％、特に７．２～２３％であることが好ましい。ＢａＯの含有量が多すぎると、成形中にＢａＯ起因の結晶が析出しやすくなる。 BaO is a component that increases the stability of vitrification and improves the weather resistance. Especially when less is P 2 O 5, to easily enjoy the effect of vitrification stability by BaO. The content of BaO is preferably 0 to 30%, 5 to 30%, 7 to 25%, particularly 7.2 to 23%. When there is too much content of BaO, the crystal | crystallization resulting from BaO will precipitate easily during shaping | molding.
　近赤外線吸収ガラスには、上記成分以外にも下記の成分を含有させることができる。 In addition to the above components, the near infrared absorbing glass may contain the following components.
　ＺｎＯはガラス化の安定性及び耐候性を改善する成分である。ＺｎＯの含有量は０～１３％、０．１～１２％、特に１～１０％であることが好ましい。ＺｎＯの含有量が多すぎると、溶融性が低下して溶融温度が高くなり、結果として所望の光学特性が得にくくなる。また、ＺｎＯ成分起因の結晶が析出しやすくなる。なお、特にＰ２Ｏ５が少ない場合に、ＺｎＯによるガラス化安定性の効果を享受しやすい。 ZnO is a component that improves the stability and weather resistance of vitrification. The content of ZnO is preferably 0 to 13%, 0.1 to 12%, particularly 1 to 10%. When there is too much content of ZnO, a meltability will fall and a melting temperature will become high, and it will become difficult to obtain a desired optical characteristic as a result. In addition, crystals due to the ZnO component are likely to precipitate. In particular, when the amount of P 2 O 5 is small, it is easy to enjoy the effect of vitrification stability due to ZnO.
　Ｎｂ２Ｏ５及びＴａ２Ｏ５は耐候性を高める成分である。Ｎｂ２Ｏ５及びＴａ２Ｏ５の各成分の含有量は０～２０％、０．１～２０％、１～１８％、特に２～１５％であることが好ましい。これらの成分の含有量が多すぎると、溶融温度が高くなって、所望の光学特性が得にくくなる。なお、Ｎｂ２Ｏ５及びＴａ２Ｏ５の合量は０～２０％、０．１～２０％、１～１８％、特に２～１５％であることが好ましい。 Nb 2 O 5 and Ta 2 O 5 are components that enhance the weather resistance. The content of each component of Nb 2 O 5 and Ta 2 O 5 is preferably 0 to 20%, 0.1 to 20%, 1 to 18%, particularly 2 to 15%. When there is too much content of these components, melting temperature will become high and it will become difficult to obtain a desired optical characteristic. The total amount of Nb 2 O 5 and Ta 2 O 5 is preferably 0 to 20%, 0.1 to 20%, 1 to 18%, particularly preferably 2 to 15%.
　ＧｅＯ２は耐候性を高める成分である。ＧｅＯ２の含有量は０～２０％、０．１～２０％、０．３～１７％、特に０．４～１５％であることが好ましい。ＧｅＯ２の含有量が少なすぎると、上記効果が得にくくなる。一方、ＧｅＯ２の含有量が多すぎると、溶融温度が高くなって、所望の光学特性が得にくくなる。 GeO 2 is a component that enhances weather resistance. The GeO 2 content is preferably 0 to 20%, 0.1 to 20%, 0.3 to 17%, particularly preferably 0.4 to 15%. When the content of GeO 2 is too small, the effect is difficult to obtain. On the other hand, when the content of GeO 2 is too large, the melting temperature becomes high and it becomes difficult to obtain desired optical characteristics.
　ＳｉＯ２はガラス骨格を強化する成分である。また、耐候性を向上させる効果がある。ＳｉＯ２の含有量は０～１０％、０．１～８％、特に１～６％であることが好ましい。ＳｉＯ２の含有量が多すぎると、かえって耐候性が低下しやすくなる。また、ガラス化が不安定になる傾向がある。 SiO 2 is a component that reinforces the glass skeleton. Moreover, there exists an effect which improves a weather resistance. The content of SiO 2 is preferably 0 to 10%, 0.1 to 8%, particularly 1 to 6%. When the content of SiO 2 is too large, rather weather resistance tends to lower. Also, vitrification tends to be unstable.
　また、上記成分以外にも、Ｂ２Ｏ３、Ｙ２Ｏ３、Ｌａ２Ｏ３、ＣｅＯ２、Ｓｂ２Ｏ３等を本発明の効果を損なわない範囲で含有させても構わない。具体的には、これらの成分の含有量は、各々０～３％、特に各々０～２％であることが好ましい。なお、フッ素を含有させることにより化学的耐久性を向上させることが可能であるが、フッ素は環境負荷物質であるため、含有しないことが好ましい。 Further, in addition to the above components also, B 2 O 3, Y 2 O 3, La 2 O 3, may be a CeO 2, Sb 2 O 3 or the like is contained in a range that does not impair the effects of the present invention. Specifically, the content of these components is preferably 0 to 3%, particularly preferably 0 to 2%. Although chemical durability can be improved by containing fluorine, fluorine is preferably not contained because it is an environmentally hazardous substance.
　近赤外線吸収ガラスの液相温度は７７０℃以下、特に７５０℃以下であることが好ましい。液相温度が高すぎると、製造工程において（特に成形時に）失透しやすくなる。 The liquid phase temperature of the near infrared ray absorbing glass is preferably 770 ° C. or lower, particularly preferably 750 ° C. or lower. If the liquidus temperature is too high, devitrification tends to occur in the manufacturing process (particularly during molding).
　上記の方法で得られた近赤外線吸収ガラスは、可視域における高い光透過率及び近赤外域における優れた光吸収特性の両者を達成することが可能となる。具体的には、波長５５０ｎｍにおける光透過率は７９％以上、特に８０％以上であることが好ましい。一方、波長７００ｎｍにおける光透過率は１３％以下、特に１１％以下であることが好ましく、波長１２００ｎｍにおける光透過率は２５％以下、特に２０％以下であることが好ましい。 The near-infrared absorbing glass obtained by the above method can achieve both high light transmittance in the visible range and excellent light absorption characteristics in the near-infrared range. Specifically, the light transmittance at a wavelength of 550 nm is preferably 79% or more, particularly preferably 80% or more. On the other hand, the light transmittance at a wavelength of 700 nm is preferably 13% or less, particularly preferably 11% or less, and the light transmittance at a wavelength of 1200 nm is preferably 25% or less, particularly preferably 20% or less.
　近赤外線吸収ガラスは、通常、板状で用いられる。厚みは０．０１～１．２ｍｍ、特に０．０５～１．２ｍｍであることが好ましい。厚みが小さすぎると、機械的強度に劣る傾向がある。一方、厚みが大きすぎると、光学デバイスの薄型化が困難になる傾向がある。 Near-infrared absorbing glass is usually used in the form of a plate. The thickness is preferably 0.01 to 1.2 mm, particularly 0.05 to 1.2 mm. If the thickness is too small, the mechanical strength tends to be inferior. On the other hand, if the thickness is too large, it is difficult to reduce the thickness of the optical device.
　以下、本発明の近赤外線吸収ガラスの製造方法を実施例に基づいて詳細に説明するが、本発明は本実施例に限定されるものではない。 Hereinafter, although the manufacturing method of the near-infrared absorption glass of this invention is demonstrated in detail based on an Example, this invention is not limited to a present Example.
　（実験１）
　質量％で、Ｐ２Ｏ５　４６．３％、Ａｌ２Ｏ３　６．６％、ＭｇＯ　２．６％、ＣａＯ　４．２％、ＢａＯ　２１．４％、Ｋ２Ｏ　１６．１％、ＣｕＯ　２．８％の組成となるように調合した原料粉末を円筒状の白金ルツボに投入し、１２００℃で加熱溶解することにより均質な溶融ガラスとした。溶融ガラスを９００℃まで冷却し、そのまま５時間保持した。次に、溶融ガラスをカーボン板上に流し出し、冷却固化した後、アニールを行った。得られた板状ガラスについて、０．５ｍｍ厚となるように両面を鏡面研磨することにより、試料ａ（近赤外線吸収ガラス）を得た。得られた試料について、分光光度計（島津製作所製ＵＶ－３１００ＰＣ）を用いて、波長３００～１３００ｎｍの範囲で光透過率を測定した。結果を図１に示す。なお、溶融ガラスの液面の面積は４４１６ｍｍ２、深さは４．５ｍｍにした。 (Experiment 1)
In mass%, P 2 O 5 46.3%, Al 2 O 3 6.6%, MgO 2.6%, CaO 4.2%, BaO 21.4%, K 2 O 16.1%, CuO 2 The raw material powder prepared so as to have a composition of 8% was put into a cylindrical platinum crucible and heated and melted at 1200 ° C. to obtain a homogeneous molten glass. The molten glass was cooled to 900 ° C. and held there for 5 hours. Next, the molten glass was poured onto a carbon plate, cooled and solidified, and then annealed. About the obtained plate glass, both surfaces were mirror-polished so that it might be set to 0.5 mm thickness, and the sample a (near-infrared absorption glass) was obtained. The light transmittance of the obtained sample was measured in the wavelength range of 300 to 1300 nm using a spectrophotometer (UV-3100PC manufactured by Shimadzu Corporation). The results are shown in FIG. The area of the liquid surface of the molten glass was 4416 mm 2 and the depth was 4.5 mm.
　一方、比較例として、溶融ガラスを９００℃で保持する工程を経なかった点を除き、上記と同様にして試料イを作製した。得られた試料について、上記と同様にして光透過率を測定した。結果を図１に示す。 On the other hand, as a comparative example, Sample A was prepared in the same manner as described above except that the step of holding the molten glass at 900 ° C. was not performed. About the obtained sample, the light transmittance was measured like the above. The results are shown in FIG.
　図１から明らかなように、実施例の試料ａは比較例の試料イと比較して可視域での光透過率が高く、また近赤外光をシャープにカットしていることがわかる。 As is apparent from FIG. 1, it can be seen that the sample a of the example has a higher light transmittance in the visible region than the sample A of the comparative example, and sharply cuts near-infrared light.
　（実験２）
　溶融ガラスの液面の面積と深さを表１の通り変化させたこと以外は、実験１と同様にして試料ｂ～ｍを作製し、波長５００ｎｍにおける光透過率を測定した。結果を表１及び図２に示す。図２にはデータプロットとともに、線形近似曲線もあわせて示している。なお、溶融ガラスの液面の面積は、使用する白金ルツボのサイズ（直径）を適宜変更することにより調整した。 (Experiment 2)
Samples b to m were prepared in the same manner as in Experiment 1 except that the liquid surface area and depth of the molten glass were changed as shown in Table 1, and the light transmittance at a wavelength of 500 nm was measured. The results are shown in Table 1 and FIG. FIG. 2 also shows a linear approximation curve together with the data plot. The area of the liquid surface of the molten glass was adjusted by appropriately changing the size (diameter) of the platinum crucible to be used.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１及び図２から明らかなように、溶融ガラスの液面の面積Ｓと深さＤの比Ｓ／Ｄが１００（ｍｍ）以上である場合、波長５００ｎｍにおいて概ね８４％以上と優れた光透過率を示した。なお、Ｓ／Ｄの値が大きくなるに従い、波長５００ｎｍにおける光透過率も向上する傾向を示した。 As is apparent from Table 1 and FIG. 2, when the ratio S / D of the liquid surface area S to the depth D is 100 (mm) or more, the light transmission is excellent at approximately 84% or more at a wavelength of 500 nm. Showed the rate. In addition, the light transmittance in wavelength 500nm showed the tendency to improve as the value of S / D became large.
　（実験３）
　溶融ガラスの液面の面積を４４１６ｍｍ２、深さを１７ｍｍにしたこと、及び、溶融ガラスを９００℃にて保持する際に、溶融ガラス中に酸素バブリングしたこと以外は、実験１と同様にして試料ｎを作製した。比較のため、酸素バブリングしなかった試料ロも作製した。これらの試料について、波長３００～１３００ｎｍの範囲で光透過率を測定した。結果を図３に示す。 (Experiment 3)
Except that the liquid surface area of the molten glass was 4416 mm 2 , the depth was 17 mm, and oxygen was bubbled into the molten glass when the molten glass was held at 900 ° C. Sample n was prepared. For comparison, a sample B that was not subjected to oxygen bubbling was also prepared. The light transmittance of these samples was measured in the wavelength range of 300 to 1300 nm. The results are shown in FIG.
　図３から明らかなように、酸素バブリングすると、可視域での光透過率が高くなった。 As is clear from FIG. 3, when oxygen was bubbled, the light transmittance in the visible range increased.

Claims (8)

  1. 　Ｐ及びＣｕを含む近赤外線吸収ガラスの製造方法であって、原料を溶融温度Ｔ１で加熱溶解して溶融ガラスにした後、溶融温度Ｔ１より低い保持温度Ｔ２で溶融ガラスを保持することを特徴とする近赤外線吸収ガラスの製造方法。 A method for producing a near-infrared absorbing glass containing P and Cu, wherein a raw material is heated and melted at a melting temperature T 1 to form a molten glass, and then the molten glass is held at a holding temperature T 2 lower than the melting temperature T 1. The manufacturing method of the near-infrared absorption glass characterized by these.
  2. 　Ｔ１－Ｔ２が１００～６００℃であることを特徴とする請求項１に記載の近赤外線吸収ガラスの製造方法。 The method for producing a near-infrared absorbing glass according to claim 1, wherein T 1 -T 2 is 100 to 600 ° C.
  3. 　Ｔ１が９００～１４００℃であることを特徴とする請求項１または２に記載の近赤外線吸収ガラスの製造方法。 3. The method for producing near-infrared absorbing glass according to claim 1, wherein T 1 is 900 to 1400 ° C.
  4. 　Ｔ２が８００～１１００℃である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線吸収ガラスの製造方法。 The method for producing a near-infrared absorbing glass according to any one of claims 1 to 3, wherein T 2 is 800 to 1100 ° C.
  5. 　近赤外線吸収ガラスが、質量％で、Ｐ２Ｏ５　２０～８０％、Ａｌ２Ｏ３　２～２０％、ＣｕＯ　０．１～２０％、Ｒ２Ｏ　０～５０％（ただし、ＲはＬｉ、Ｎａ及びＫから選択される少なくとも１種）、Ｒ’Ｏ　０～５０％（ただし、Ｒ’はＭｇ、Ｃａ、Ｓｒ及びＢａから選択される少なくとも１種）を含有することを特徴とする請求項１～４のいずれか一項に記載の近赤外線吸収ガラスの製造方法。 Near-infrared absorbing glass is, by mass%, P 2 O 5 20-80%, Al 2 O 3 2-20%, CuO 0.1-20%, R 2 O 0-50% (where R is Li, And at least one selected from Na and K), R′O 0 to 50% (wherein R ′ is at least one selected from Mg, Ca, Sr and Ba). The method for producing a near-infrared absorbing glass according to any one of 1 to 4.
  6. 　保持温度Ｔ２で溶融ガラスを保持する際の溶融ガラスの液面の面積をＳ（ｍｍ２）、溶融ガラスの深さをＤ（ｍｍ）とした場合、Ｓ／Ｄ≧１００（ｍｍ）の関係を満たすことを特徴とする請求項１～５のいずれか一項に記載の近赤外線吸収ガラスの製造方法。 The relationship of S / D ≧ 100 (mm) where S (mm 2 ) is the liquid surface area of the molten glass when holding the molten glass at the holding temperature T 2 and D (mm) is the depth of the molten glass. The method for producing a near-infrared absorbing glass according to any one of claims 1 to 5, wherein:
  7. 　保持温度Ｔ２で溶融ガラスを保持する際に、溶融ガラス中に酸素をバブリングすることを特徴とする請求項１～６のいずれか一項に記載の近赤外線吸収ガラスの製造方法。 When holding the molten glass at the holding temperature T 2, the method of producing the near-infrared-absorbing glass as claimed in any one of claims 1 to 6, characterized in that bubbling oxygen into molten glass.
  8. 　原料を溶融温度Ｔ１で加熱溶解して溶融ガラスを得るための溶融槽と、溶融温度Ｔ１より低い保持温度Ｔ２で溶融ガラスを保持するための保持槽と、を有することを特徴とする近赤外線吸収ガラスの製造装置。 A melting tank for obtaining a molten glass by heating and melting the raw material at a melting temperature T 1 and a holding tank for holding the molten glass at a holding temperature T 2 lower than the melting temperature T 1 are provided. Near-infrared absorbing glass manufacturing equipment.
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