JP2005097067A - Light transmissive phosphate glass - Google Patents
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- 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
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- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
Abstract
Description
本発明は、光透過ガラスに関し、特定波長の光透過率の減少が抑制された光透過リン酸塩ガラスに関する。 The present invention relates to a light transmissive glass, and relates to a light transmissive phosphate glass in which a decrease in light transmittance at a specific wavelength is suppressed.
波長４０５ｎｍの紫外線または紫外線に近い可視光線は、レーザーダイオードの利用により、光磁気記憶媒体への情報入出力などに使用されており、記憶容量を増加させるためには、さらに短波長側の３６０ｎｍの光も実用化が検討されている。また紫外線は、その他に硬化化学反応、殺菌・消毒等にも使用されており、この使用において、紫外線はガラスを通じて照射され、ガラスには、紫外透過特性が要求される。 Ultraviolet light having a wavelength of 405 nm or visible light close to ultraviolet light is used for information input / output to a magneto-optical storage medium by using a laser diode, and in order to increase the storage capacity, the wavelength of 360 nm on the shorter wavelength side is further increased. The practical application of light is also being studied. In addition, ultraviolet rays are also used for curing chemical reactions, sterilization / disinfection, and the like. In this use, ultraviolet rays are irradiated through glass, and the glass is required to have ultraviolet transmission characteristics.
紫外線を透過するガラスの一種としてリン酸塩ガラスがあるが、これに紫外線を照射すると、リン酸塩ガラスから完全に除去することができない鉄イオン等の存在により、この鉄イオン等がガラス内部で酸化・還元反応を起こし、紫外線透過率を著しく減少させるソラリゼーションが生じることになる。このことは、種々の技術文献（ガラス工学ハンドブック（朝倉書店、１９６３）等）においても報告がなされている。このようにリン酸塩ガラスに長時間紫外線を照射すると、リン酸塩ガラスの紫外線透過率が低下するため、連続して紫外線にさらされる状況下でリン酸塩ガラスを使用することは、適しているものとは言えない。 Phosphate glass is one type of glass that transmits ultraviolet light. When this glass is irradiated with ultraviolet light, the presence of iron ions that cannot be completely removed from the phosphate glass causes the iron ions to be contained inside the glass. Solarization that causes an oxidation / reduction reaction and significantly reduces the ultraviolet transmittance occurs. This has been reported in various technical documents (Glass Engineering Handbook (Asakura Shoten, 1963), etc.). When the phosphate glass is irradiated with ultraviolet rays for a long time in this way, the ultraviolet transmittance of the phosphate glass decreases, so it is appropriate to use the phosphate glass under continuous exposure to ultraviolet rays. It cannot be said that it is.
そこで、リン酸塩ガラスの耐ソラリゼーション性を高めるための検討がなされており、例えば、特許文献１に耐ソラリゼーション性リン酸塩ガラスに関する発明が記載されている。
特許文献１に記載された発明は、Ｂａ２Ｐ２Ｏ7、Ａｌ（ＰＯ３）３、ＢａＦ２、ＡｌＦ３、Ｆｅ及びＣｒからなる化合物を溶融して得られるリン酸塩ガラスである。このリン酸塩ガラスは、耐ソラリゼーションが良好との報告がなされている。 The invention described in Patent Document 1 is a phosphate glass obtained by melting a compound composed of Ba 2 P 2 O 7 , Al (PO 3 ) 3 , BaF 2 , AlF 3 , Fe and Cr. This phosphate glass has been reported to have good solarization resistance.
本発明者は、特許文献１に記載されたリン酸塩ガラスとは異なる化合物を原料に使用し、リン酸塩ガラスの紫外線透過率減少抑制を検討してきた。即ち本発明の目的は、紫外線を照射しても紫外線透過率の減少が抑制される紫外線透過リン酸塩ガラスを提供することにある。 The present inventor has used a compound different from the phosphate glass described in Patent Document 1 as a raw material, and has been studying suppression of UV transmittance reduction of the phosphate glass. That is, an object of the present invention is to provide an ultraviolet transmissive phosphate glass in which a decrease in ultraviolet transmittance is suppressed even when irradiated with ultraviolet rays.
本発明者は、上記の課題を解決するため、リン酸塩ガラスに所定の遷移元素及び希土類元素のうち一方または双方をリン酸塩ガラスに含有させることにより、紫外線透過率の減少を抑制または、紫外線透過率を増加できることを見出し、本発明を完成するに至った。 In order to solve the above problems, the present inventor suppresses a decrease in ultraviolet transmittance by allowing phosphate glass to contain one or both of predetermined transition elements and rare earth elements in phosphate glass, or The present inventors have found that the ultraviolet transmittance can be increased and have completed the present invention.
即ち、本発明は、希土類元素一種又は二種以上を含有することを特徴とする紫外線透過性リン酸塩ガラスである。 That is, the present invention is an ultraviolet light transmissive phosphate glass containing one or more rare earth elements.
また、本発明は、希土類元素一種又は二種以上を含有することを特徴とする波長３５０〜３７０ｎｍ又は３９０〜４２０ｎｍの光透過リン酸塩ガラスである。 Moreover, this invention is a light transmission phosphate glass with a wavelength of 350-370 nm or 390-420 nm characterized by containing 1 type, or 2 or more types of rare earth elements.
リン酸塩ガラスに希土類元素を含有させることにより、３００〜５００ｎｍの光を照射しても、その波長における光透過率の減少が抑制されたリン酸塩ガラスとなる。 By including rare earth elements in the phosphate glass, a phosphate glass in which a decrease in light transmittance at that wavelength is suppressed even when irradiated with light of 300 to 500 nm is obtained.
また光情報記憶媒体への情報入出力に使用又は使用が検討されている４０５ｎｍ又は３６０ｎｍの光に対しても使用可能であり、この使用に要求される波長３５０〜３７０ｎｍ又は３９０〜４２０ｎｍの範囲の波長光を透過することができるリン酸塩ガラスとして好適である。 It can also be used for light of 405 nm or 360 nm that is being considered for use or input / output to / from optical information storage media, and has a wavelength range of 350 to 370 nm or 390 to 420 nm required for this use. It is suitable as a phosphate glass capable of transmitting wavelength light.
本発明は、希土類元素一種以上とバナジウム、ニッケル、コバルト、クロム及び銅の群から選ばれる遷移金属一種以上を含有することを特徴とする光透過リン酸塩ガラスである。本発明のリン酸塩ガラスは、波長３００〜４５０ｎｍの光を継続して照射した場合であっても、ガラスの紫外線透過率の減少が抑制されるか又は上昇するリン酸塩ガラスである。 The present invention is a light-transmitting phosphate glass characterized by containing one or more rare earth elements and one or more transition metals selected from the group of vanadium, nickel, cobalt, chromium and copper. The phosphate glass of the present invention is a phosphate glass in which a decrease in the ultraviolet transmittance of the glass is suppressed or increased even when light having a wavelength of 300 to 450 nm is continuously irradiated.
また、本発明は、希土類元素一種以上とバナジウム、ニッケル、コバルト、クロム及び銅の群から選ばれる遷移金属一種以上を含有することを特徴とする波長３５０〜３７０ｎｍ又は３９０〜４２０ｎｍの光透過リン酸塩ガラスである。光情報記憶媒体への情報入出力に使用又は使用が検討されている４０５ｎｍ又は３６０ｎｍの光に対しても使用可能であり、この使用に要求される波長３５０〜３７０ｎｍ又は３９０〜４２０ｎｍの範囲の波長光を透過することができるリン酸塩ガラスとして好適である。 The present invention also includes a light-transmitting phosphoric acid having a wavelength of 350 to 370 nm or 390 to 420 nm, comprising one or more rare earth elements and one or more transition metals selected from the group of vanadium, nickel, cobalt, chromium and copper It is salt glass. It can also be used for light of 405 nm or 360 nm that is being used or studied for input / output of information to and from an optical information storage medium, and a wavelength in the range of 350 to 370 nm or 390 to 420 nm required for this use. It is suitable as a phosphate glass that can transmit light.
これら、希土類元素一種以上と所定の遷移金属一種以上を含有するリン酸塩ガラスに所定波長の光を照射しても、光透過率の減少が抑制されるのは、光透過率の減少につながるガラス内部の劣化が起こらないためであると考えられる。また、光透過率が上昇するリン酸塩ガラスの場合、リン酸塩ガラス表面に埃等が付着して光透過率が減少することになるが、リン酸塩ガラス自体の透過率上昇によって、前記光透過率の減少が相殺又は半減されることになる。 Even if the phosphate glass containing one or more rare earth elements and one or more transition metals is irradiated with light of a predetermined wavelength, the decrease in the light transmittance is suppressed, resulting in a decrease in the light transmittance. This is probably because the glass does not deteriorate inside. In addition, in the case of phosphate glass that increases the light transmittance, dust or the like adheres to the phosphate glass surface and the light transmittance decreases, but due to the increase in the transmittance of the phosphate glass itself, The decrease in light transmittance will be offset or halved.
前記希土類元素は、ランタン、セリウム、プラセオジウム、ネオジム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、ルテチウム、スカンジウム、イットリウム等、特に限定されない。 The rare earth element is not particularly limited, such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium, scandium, yttrium, and the like.
リン酸塩ガラスに含有させるには、例えば、Ｌａ２Ｏ３、Ｐｒ６Ｏ１１、Ｎｄ２Ｏ３、Ｓｍ２Ｏ３、Ｅｕ２Ｏ３、Ｇｄ２Ｏ３、Ｔｂ４Ｏ７、Ｈｏ２Ｏ３、Ｅｒ２Ｏ３、Ｔｍ２Ｏ３、Ｌｕ２Ｏ３、Ｓｃ２Ｏ３、Ｙ２Ｏ３等の希土類元素の酸化物を溶融して含有させると良い。リン酸塩ガラスの紫外線透過率を高透過率とする場合には、その紫外線吸収が小さな希土類元素を適宜選択することになる。例えば、Ｐｒ６Ｏ１１、Ｎｄ２Ｏ３、Ｓｍ２Ｏ３、Ｅｕ２Ｏ３、Ｈｏ２Ｏ３等を選択し、これをリン酸塩ガラスに含ませると良い。希土類元素酸化物の含有量は、０．０５〜１０重量％リン酸塩ガラスに含有させるべきである。 The inclusion in the phosphate glass, for example, La 2 O 3, Pr 6 O 11, Nd 2 O 3, Sm 2 O 3, Eu 2 O 3, Gd 2 O 3, Tb 4 O 7, Ho 2 O 3 , oxides of rare earth elements such as Er 2 O 3 , Tm 2 O 3 , Lu 2 O 3 , Sc 2 O 3 , Y 2 O 3 may be melted and contained. When the ultraviolet transmittance of the phosphate glass is set to a high transmittance, a rare earth element having a small ultraviolet absorption is appropriately selected. For example, Pr 6 O 11 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Ho 2 O 3 and the like may be selected and included in the phosphate glass. The content of rare earth element oxide should be contained in 0.05 to 10% by weight phosphate glass.
前記リン酸塩ガラスにバナジウム、ニッケル、コバルト、クロム及び銅の群から選ばれる一種以上の遷移金属を含有させるには、例えば、前記遷移金属酸化物であるＶ２Ｏ５、ＮｉＯ、Ｃｏ２Ｏ３、Ｋ２Ｃｒ２Ｏ７、Ｃｒ２Ｏ３及びＣｕＯのうち一種以上を選定し、これを溶融してガラスに含有させることができる。 In order for the phosphate glass to contain one or more transition metals selected from the group consisting of vanadium, nickel, cobalt, chromium, and copper, for example, the transition metal oxides V 2 O 5 , NiO, Co 2 O 3 , one or more of K 2 Cr 2 O 7 , Cr 2 O 3 and CuO can be selected and melted to be contained in the glass.
Ｖ２Ｏ５を選定した場合には、ガラスの液相温度を低下させ、より低温での結晶化を防ぐことができる。これら遷移金属酸化物は、リン酸塩ガラス中に０．０５〜１０重量％含有させるべきであり、０．０５〜５重量％の含有量であると、より好適である。０．０５重量％以下であると、紫外線透過率減少抑制を示すものの、明らかな紫外線透過率上昇の効果を生じない。一方、１０重量％以上であると、前記遷移金属固有の紫外線吸収によって、リン酸塩ガラスの紫外線透過率が低くなる。 When V 2 O 5 is selected, the liquidus temperature of the glass can be lowered and crystallization at a lower temperature can be prevented. These transition metal oxides should be contained in the phosphate glass in an amount of 0.05 to 10% by weight, and more preferably 0.05 to 5% by weight. When it is 0.05% by weight or less, although the UV transmittance decrease is suppressed, the effect of clearly increasing the UV transmittance is not produced. On the other hand, if it is 10% by weight or more, the ultraviolet transmittance of the phosphate glass is lowered due to the ultraviolet absorption inherent in the transition metal.
また、本発明のリン酸塩ガラスは、バナジウムを含有することを特徴とする波長３５０〜４００ｎｍの光透過リン酸塩ガラスである。このリン酸塩ガラスは、波長３５０〜４００ｎｍの光を連続照射しても、当該波長域の光透過率の減少が抑制されるか又は透過率が上昇するリン酸塩ガラスである。 The phosphate glass of the present invention is a light-transmitting phosphate glass having a wavelength of 350 to 400 nm characterized by containing vanadium. This phosphate glass is a phosphate glass in which a decrease in light transmittance in the wavelength region is suppressed or the transmittance is increased even when light having a wavelength of 350 to 400 nm is continuously irradiated.
このリン酸塩ガラスに、波長３５０〜４００ｎｍの光を照射しても、光透過率の減少が抑制されるのは、光透過率の減少につながるガラス内部の劣化が起こらないためであると考えられる。また、光透過率が上昇するリン酸塩ガラスの場合、リン酸塩ガラス表面に埃等が付着して、光透過率が減少することになるが、リン酸塩ガラス自体の透過率上昇によって、前記光透過率が減少することが相殺又は半減されることになる。 Even if this phosphate glass is irradiated with light having a wavelength of 350 to 400 nm, the decrease in the light transmittance is suppressed because there is no deterioration in the glass leading to a decrease in the light transmittance. It is done. In addition, in the case of phosphate glass with increased light transmittance, dust or the like adheres to the surface of the phosphate glass and the light transmittance decreases, but by increasing the transmittance of the phosphate glass itself, The decrease in the light transmittance is offset or halved.
バナジウムは、例えば、酸化物であるＶ２Ｏ５を溶融してガラスに含有させることができる。Ｖ２Ｏ５は、リン酸塩ガラス中に０．０５〜１０重量％含有させるべきである。このリン酸塩ガラスは、バナジウムを含んでいないリン酸塩ガラスよりもガラスの液相温度が低く、より低温での結晶化を防ぐことができる。 For example, vanadium can be melted and contained in glass by V 2 O 5 which is an oxide. V 2 O 5 should be contained from 0.05 to 10 wt% in the phosphate glass. This phosphate glass has a lower liquidus temperature than phosphate glass not containing vanadium, and can prevent crystallization at a lower temperature.
前記リン酸塩ガラス中のＰ２Ｏ５は、４０〜９０重量％含有されていれば良い。また本発明のリン酸塩ガラスに、Ａｌ２Ｏ３及びＺｎＯの一方又は双方を含有させると良い。これらの化合物を溶融してガラスに含ませれば、リン酸塩ガラスの耐水性を向上させることができる。リン酸塩ガラスに、Ａｌ２Ｏ３を含有させる場合には、２〜１８重量％含有させれば良く、ＺｎＯを含有させる場合には、２０重量％以下含有させれば良い。これらの化合物の含有量が下限値未満である場合、リン酸塩ガラスの耐水性が乏しくなる傾向があり、上限値を超える場合、リン酸塩ガラスの溶融温度が高くなる傾向がある。また、Ｂ２Ｏ３を１５重量％以下含有させても良い。
P 2 O 5 in the phosphate glass may be contained in an amount of 40 to 90% by weight. Also in phosphate glass of the present invention, it may be contained one or both of Al 2 O 3 and ZnO. If these compounds are melted and contained in the glass, the water resistance of the phosphate glass can be improved. When Al 2 O 3 is contained in the phosphate glass, it may be contained at 2 to 18% by weight, and when ZnO is contained, it may be contained at 20% by weight or less. When the content of these compounds is less than the lower limit, the water resistance of the phosphate glass tends to be poor, and when it exceeds the upper limit, the melting temperature of the phosphate glass tends to increase. Further,
また本発明のリン酸塩ガラスには、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢａＯの群から選ばれる一種以上を含有させると良い。含有量として、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏのうち一種以上を含ませる場合には、２５重量％以下であり、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢａＯの群から選ばれる一種以上を含有させる場合には、２〜２５重量％である。 The phosphate glass of the present invention may contain one or more selected from the group consisting of Li 2 O, Na 2 O, K 2 O, MgO, CaO, SrO and BaO. The content, Li 2 O, if the inclusion of one or more of Na 2 O and K 2 O is more than 25 wt%, MgO, CaO, to contain one or more selected from the group of SrO and BaO In some cases, it is 2 to 25% by weight.
以上の本発明によれば、希土類元素をリン酸塩ガラスに含有させることにより、３００〜５００ｎｍの紫外線を含む光を照射した場合であっても、光透過率の減少を抑制したリン酸ガラスの提供を実現することができる。また、遷移金属と希土類元素を含有するリン酸塩ガラスであれば、３００ｎｍ〜４５０ｎｍの波長光を照射しても、この波長範囲の光透過率減少を抑制又は光透過率が上昇するリン酸塩ガラスとなる。また、バナジウムを含有するリン酸塩ガラスによれば、波長３５０〜４００ｎｍの光を連続して照射しても、この波長域での光透過率の減少が抑制又は光透過率が上昇するリン酸塩ガラスとなる。 According to the present invention described above, the phosphate glass containing the rare earth element contained in the phosphate glass suppresses a decrease in light transmittance even when irradiated with light including ultraviolet rays of 300 to 500 nm. Offering can be realized. Moreover, if it is a phosphate glass containing a transition metal and a rare earth element, a phosphate that suppresses a decrease in light transmittance in this wavelength range or increases the light transmittance even when irradiated with light having a wavelength of 300 nm to 450 nm. It becomes glass. In addition, according to the phosphate glass containing vanadium, phosphoric acid that suppresses a decrease in light transmittance in this wavelength range or increases the light transmittance even when continuously irradiated with light having a wavelength of 350 to 400 nm. It becomes salt glass.
以下、本発明を実施例に基づいて本発明の実施の形態を詳細に説明するが、実施例における具体的な記載内容は、特に本発明を限定するものではない。 Hereinafter, the present invention will be described in detail based on examples, but the specific description in the examples does not particularly limit the present invention.
実施例において、各ガラス原料を調合後、ＳｉＣ発熱体の電気炉で１２５０〜１４００℃で溶融し、この溶融ガラスをカーボンに流し込みハンドプレスをして急冷し、徐冷炉で歪をとることにより、リン酸塩ガラスを製造した。このリン酸塩ガラスを電気炉で５００〜６５０℃の温度で３０分間熱処理を行った後、研磨処理を施した。実施例のリン酸塩ガラス原料の調合組成、ガラス組成は以下の通りである。 In the examples, after preparing each glass raw material, it was melted at 1250 to 1400 ° C. in an SiC heating element electric furnace, poured into carbon, rapidly cooled by hand pressing, and strained in a slow cooling furnace to obtain phosphorus. An acid salt glass was produced. This phosphate glass was subjected to a heat treatment in an electric furnace at a temperature of 500 to 650 ° C. for 30 minutes and then subjected to a polishing treatment. The preparation composition and glass composition of the phosphate glass raw material of the examples are as follows.
Ａｌ（ＰＯ３）３：３６．３重量部、ＫＨ２ＰＯ４：８．７重量部、ＣａＨ２Ｐ２Ｏ７：２７．３重量部、Ｂａ（ＰＯ３）２：１５．８重量部、ＢａＣＯ３：１０．５重量部、Ｚｎ３（ＰＯ４）２：６．８重量部、Ｐｒ６Ｏ１１：０．５重量部
（２）リン酸塩ガラス組成
上記ガラス原料調合組成によって、製造したガラスの成分組成は、次の通りである。このリン酸塩ガラスの研磨後の厚みは、２．０５ｍｍであった。
Ｐ２Ｏ５：６１．８６重量部、Ａｌ２Ｏ３：７．０１重量部、Ｋ２Ｏ：３．００重量部、ＣａＯ：７．１０重量部、ＢａＯ：１６．２６重量部、ＺｎＯ：４．３０重量部、Ｐｒ６Ｏ１１：０．５重量部
Al (PO 3 ) 3 : 36.3 parts by weight, KH 2 PO 4 : 8.7 parts by weight, CaH 2 P 2 O 7 : 27.3 parts by weight, Ba (PO 3 ) 2 : 15.8 parts by weight, BaCO 3 : 10.5 parts by weight, Zn 3 (PO 4 ) 2 : 6.8 parts by weight, Pr 6 O 11 : 0.5 parts by weight (2) Phosphate glass composition The component composition of glass is as follows. The thickness of this phosphate glass after polishing was 2.05 mm.
P 2 O 5 : 61.86 parts by weight, Al 2 O 3 : 7.01 parts by weight, K 2 O: 3.00 parts by weight, CaO: 7.10 parts by weight, BaO: 16.26 parts by weight, ZnO: 4.30 parts by weight, Pr 6 O 11: 0.5 parts by weight
（１）ガラス原料調合組成
（ＮＨ４）２ＨＰＯ４：９．１重量部、Ａｌ（ＰＯ３）３：３６．３重量部、ＫＨ２ＰＯ４：８．７重量部、ＣａＨ２Ｐ２Ｏ７：２７．３重量部、ＢａＣＯ３：２０．９重量部、Ｚｎ３（ＰＯ４）２：６．８重量部、Ｖ２Ｏ５：０．２重量部、Ｈｏ２Ｏ３：３重量部
（２）リン酸塩ガラス組成
上記ガラス原料調合組成によって、製造したガラスの成分組成は、次の通りである。このリン酸塩ガラスの研磨後の厚みは、２．０５ｍｍであった。
Ｐ２Ｏ５：５９．１６重量部、Ａｌ２Ｏ３：７．０１重量部、Ｋ２Ｏ：３．００重量部、ＣａＯ：７．１０重量部、ＢａＯ：１６．２４重量部、ＺｎＯ：４．３０重量部、Ｖ２Ｏ５：０．２０重量部、Ｈｏ２Ｏ３：３．００重量部
(1) Glass raw material preparation composition (NH 4 ) 2 HPO 4 : 9.1 parts by weight, Al (PO 3 ) 3 : 36.3 parts by weight, KH 2 PO 4 : 8.7 parts by weight, CaH 2 P 2 O 7 : 27.3 parts by weight, BaCO 3 : 20.9 parts by weight, Zn 3 (PO 4 ) 2 : 6.8 parts by weight, V 2 O 5 : 0.2 parts by weight, Ho 2 O 3 : 3 parts by weight (2) Phosphate glass composition The component composition of the glass produced by the above glass raw material preparation composition is as follows. The thickness of this phosphate glass after polishing was 2.05 mm.
P 2 O 5 : 59.16 parts by weight, Al 2 O 3 : 7.01 parts by weight, K 2 O: 3.00 parts by weight, CaO: 7.10 parts by weight, BaO: 16.24 parts by weight, ZnO: 4.30 parts by weight, V 2 O 5 : 0.20 parts by weight, Ho 2 O 3 : 3.00 parts by weight
（１）ガラス原料調合組成
Ａｌ（ＰＯ３）３：４１．４５重量部、ＫＨ２ＰＯ４：３１．８０重量部、ＭｇＣＯ３：２．８５重量部、Ｍｇ（ＰＯ３）２：５．５５重量部、ＣａＨ２Ｐ２Ｏ７：１５．１０重量部、ＢａＣＯ３：１１．９０重量部、（ＣＯＯＨ）２：０．２０重量部、Ｖ２Ｏ５：０．１０重量部、Ｐｒ６Ｏ１１：１．００重量部
（２）リン酸塩ガラス組成
上記ガラス原料調合組成によって、製造したガラスの成分組成は、次の通りである。このリン酸塩ガラスの研磨後の厚みは、１．４０ｍｍであった。
Ｐ２Ｏ５：６４．２９重量部、Ａｌ２Ｏ３：７．９９重量部、Ｋ２Ｏ：１０．９８重量部、ＭｇＯ：２．５９重量部、ＣａＯ：３．９２重量部、ＢａＯ：９．２４重量部、Ｖ２Ｏ５：０．１０重量部、Ｐｒ６Ｏ１１：１．００重量部
(1) Glass raw material preparation composition Al (PO 3 ) 3 : 41.45 parts by weight, KH 2 PO 4 : 31.80 parts by weight, MgCO 3 : 2.85 parts by weight, Mg (PO 3 ) 2 : 5.55 Parts by weight, CaH 2 P 2 O 7 : 15.10 parts by weight, BaCO 3 : 11.90 parts by weight, (COOH) 2 : 0.20 parts by weight, V 2 O 5 : 0.10 parts by weight, Pr 6 O 11 : 1.00 weight part (2) Phosphate glass composition The component composition of the glass manufactured by the said glass raw material preparation composition is as follows. The thickness of this phosphate glass after polishing was 1.40 mm.
P 2 O 5 : 64.29 parts by weight, Al 2 O 3 : 7.9 parts by weight, K 2 O: 10.98 parts by weight, MgO: 2.59 parts by weight, CaO: 3.92 parts by weight, BaO: 9.24 parts by weight, V 2 O 5 : 0.10 parts by weight, Pr 6 O 11 : 1.00 parts by weight
（１）ガラス原料調合組成
Ａｌ（ＰＯ３）３：４１．４５重量部、ＫＨ２ＰＯ４：３１．８重量部、ＭｇＣＯ３：２．３重量部、Ｍｇ（ＰＯ３）２：６．７重量部、ＣａＨ２Ｐ２Ｏ７：１５．１重量部、ＢａＣＯ３：１１．９重量部、Ｖ２Ｏ５：０．１重量部、
（２）リン酸塩ガラス組成
上記ガラス原料調合組成によって、製造したガラスの成分組成は、次の通りである。このリン酸塩ガラスの研磨後の厚みは、１．４６ｍｍであった。
Ｐ２Ｏ５：６５．１９重量部、Ａｌ２Ｏ３：８．００重量部、Ｋ２Ｏ：１０．９９重量部、ＭｇＯ：２．５８重量部、ＣａＯ：３．９３重量部、ＢａＯ：９．２５重量部、Ｖ２Ｏ５：０．１０重量部、
(1) Glass raw material preparation composition Al (PO 3 ) 3 : 41.45 parts by weight, KH 2 PO 4 : 31.8 parts by weight, MgCO 3 : 2.3 parts by weight, Mg (PO 3 ) 2 : 6.7 Parts by weight, CaH 2 P 2 O 7 : 15.1 parts by weight, BaCO 3 : 11.9 parts by weight, V 2 O 5 : 0.1 parts by weight,
(2) Phosphate glass composition The component composition of the glass produced by the above glass raw material preparation composition is as follows. The thickness of this phosphate glass after polishing was 1.46 mm.
P 2 O 5 : 65.19 parts by weight, Al 2 O 3 : 8.00 parts by weight, K 2 O: 10.99 parts by weight, MgO: 2.58 parts by weight, CaO: 3.93 parts by weight, BaO: 9.25 parts by weight, V 2 O 5 : 0.10 parts by weight,
（１）ガラス原料配合組成
Ａｌ（ＰＯ３）３：４１．４５重量部、ＫＨ２ＰＯ４：２３．７０重量部、ＫＮＯ３：６．００重量部、ＭｇＣＯ３：２．９０重量部、Ｍｇ（ＰＯ３）２：５．４０重量部、ＣａＨ２Ｐ２Ｏ７：１５．１０重量部、ＢａＣＯ３：１１．９０重量部、ＮｉＯ：１．４０重量部、Ｖ２Ｏ５：０．３０重量部、Ｋ２Ｃｒ２Ｏ７：０．４０重量部、Ｐｒ６Ｏ１１：３．００重量部
（２）リン酸塩ガラス組成
上記ガラス原料調合組成によって、製造したガラスの成分組成は、次の通りである。このリン酸塩ガラスの研磨後の厚みは、０．３４ｍｍであった。
Ｐ２Ｏ５：６０．０８重量部、Ａｌ２Ｏ３：８．０２重量部、Ｋ２Ｏ：１１．０２重量部、ＭｇＯ：２．５９重量部、ＣａＯ：３．９４重量部、ＢａＯ：９．２４重量部、ＮｉＯ：１．４０重量部、Ｖ２Ｏ５：０．３０重量部、Ｋ２Ｃｒ２Ｏ７：０．４０重量部、Ｐｒ６Ｏ１１：３．０１重量部
実施例１〜４で得られたガラスを、次の試験例１により、光を照射して光透過率の経時変化を測定した。また、実施例５で得られたガラスを、試験例２によって光透過率の経時変化を測定した。
（試験例１）
光照射ランプ：高圧水銀灯（３００Ｗ、オ−ク製作所製ＵＶ−３００）
照射波長：２５０〜５００ｎｍ
照射距離：１００ｍｍ
透過率測定機器：分光光度計
測定温度：室温
光照射は、コンデンサーレンズで集光させることにより行った。
透過率の測定波長及び照射時間は、次表１に示すとおり行った。
(1) Glass raw material blending composition Al (PO 3 ) 3 : 41.45 parts by weight, KH 2 PO 4 : 23.70 parts by weight, KNO 3 : 6.00 parts by weight, MgCO 3 : 2.90 parts by weight, Mg (PO 3 ) 2 : 5.40 parts by weight, CaH 2 P 2 O 7 : 15.10 parts by weight, BaCO 3 : 11.90 parts by weight, NiO: 1.40 parts by weight, V 2 O 5 : 0.30 Parts by weight, K 2 Cr 2 O 7 : 0.40 parts by weight, Pr 6 O 11 : 3.00 parts by weight (2) Phosphate glass composition The composition of the glass produced by the above glass raw material preparation composition is as follows. It is as follows. The thickness of this phosphate glass after polishing was 0.34 mm.
P 2 O 5 : 60.08 parts by weight, Al 2 O 3 : 8.02 parts by weight, K 2 O: 11.02 parts by weight, MgO: 2.59 parts by weight, CaO: 3.94 parts by weight, BaO: 9.24 parts by weight, NiO: 1.40 parts by weight, V 2 O 5 : 0.30 parts by weight, K 2 Cr 2 O 7 : 0.40 parts by weight, Pr 6 O 11 : 3.01 parts by weight The glass obtained in 1 to 4 was irradiated with light according to the following Test Example 1, and the change with time in light transmittance was measured. Moreover, the time-dependent change of the light transmittance was measured by Test Example 2 for the glass obtained in Example 5.
(Test Example 1)
Light irradiation lamp: High-pressure mercury lamp (300 W, UV-300 manufactured by Oak Seisakusho)
Irradiation wavelength: 250-500 nm
Irradiation distance: 100mm
Transmittance measuring instrument: Spectrophotometer Measurement temperature: Room temperature light irradiation was performed by condensing with a condenser lens.
The measurement wavelength of the transmittance and the irradiation time were as shown in Table 1 below.
（試験例２）
光照射ランプ：キセノンランプ（４５０Ｗ）
照射距離：３００ｍｍ
照射時間：２００時間
透過率測定装置：分光光度計
透過率測定波長：３５０〜４５０ｎｍ
測定温度：室温
試験例１及び２で得られた結果について、図１〜４は、試験例１又は２で得られた測定値から得られるグラフである。次表２は、試験例１における測定値であり、表３は、試験例2における測定値である。
(Test Example 2)
Light irradiation lamp: Xenon lamp (450W)
Irradiation distance: 300mm
Irradiation time: 200 hours Transmittance measuring device: Spectrophotometer transmittance measuring wavelength: 350-450 nm
Measurement Temperature: Room Temperature Regarding the results obtained in Test Examples 1 and 2, FIGS. 1 to 4 are graphs obtained from the measurement values obtained in Test Example 1 or 2. FIG. Table 2 below shows measured values in Test Example 1, and Table 3 shows measured values in Test Example 2.
実施例１のリン酸塩ガラスは、光照射前後において、波長３００〜５００ｎｍの透過率が、ほぼ同程度であり、光透過率の減少が抑制されていることが確認できた。 In the phosphate glass of Example 1, the transmittance at a wavelength of 300 to 500 nm was approximately the same before and after the light irradiation, and it was confirmed that the decrease in the light transmittance was suppressed.
実施例２のリン酸塩ガラスは、光照射前後において、波長３００〜５００ｎｍの光透過率が、ほぼ同程度であり、光透過率の減少が抑制されていることが確認できた。また、波長３００〜３９０ｎｍの紫外線透過率は、上昇していることが確認された。 The phosphate glass of Example 2 had substantially the same light transmittance at a wavelength of 300 to 500 nm before and after light irradiation, and it was confirmed that a decrease in light transmittance was suppressed. Further, it was confirmed that the ultraviolet transmittance at a wavelength of 300 to 390 nm was increased.
実施例３のリン酸塩ガラスも、試験後の波長４００〜５００ｎｍの全波長域において、光透過率が試験前と同程度又は上昇していた。一方、実施例４のリン酸塩ガラスは、希土類元素を含有していないものであるが、波長３５０〜４００ｎｍの透過率が、試験後には上昇していた。 The phosphate glass of Example 3 also had the same or higher light transmittance as that before the test in the entire wavelength range of 400 to 500 nm after the test. On the other hand, although the phosphate glass of Example 4 does not contain a rare earth element, the transmittance at a wavelength of 350 to 400 nm increased after the test.
実施例５のリン酸塩ガラスは、波長３５０〜４５０ｎｍの光透過率が、総じて上昇していた。 In the phosphate glass of Example 5, the light transmittance at a wavelength of 350 to 450 nm was generally increased.
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| JP2018188353A (en) * | 2017-04-28 | 2018-11-29 | ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ | Filter glass |
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| JPS55109241A (en) * | 1979-02-09 | 1980-08-22 | Hoya Corp | Production of phosphate glass having good transmission in short-wave region |
| JPS60235740A (en) * | 1984-04-18 | 1985-11-22 | シヨツト グラスヴエルケ | Glass for optical colored filter |
| JPH01286935A (en) * | 1988-05-12 | 1989-11-17 | Minolta Camera Co Ltd | Ultraviolet transmission glass |
| JPH0393647A (en) * | 1989-09-01 | 1991-04-18 | Minolta Camera Co Ltd | Ultraviolet ray transmitting glass |
| JPH0455337A (en) * | 1990-06-21 | 1992-02-24 | Ohara Inc | Ultraviolet ray transmitting glass |
| JPH06107428A (en) * | 1990-10-05 | 1994-04-19 | Carl Zeiss:Fa | Alumphosphate glass containing copper oxide ii |
| JPH11268927A (en) * | 1998-03-20 | 1999-10-05 | Hoya Corp | Phosphate glass for precision molding, optical element using the same, and production of optical element |
| JP2002055201A (en) * | 2000-08-11 | 2002-02-20 | Hoya Corp | Optical recording reproducing optical system and optical information recording and reproducing device |
| JP2002211951A (en) * | 2001-01-11 | 2002-07-31 | Okamoto Glass Co Ltd | Infrared ray-shielding green glass |
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|---|---|---|---|---|
| JPS55109242A (en) * | 1979-02-09 | 1980-08-22 | Hoya Corp | Fluorophosphate glass substantially free of bubble and production thereof |
| JPS55109241A (en) * | 1979-02-09 | 1980-08-22 | Hoya Corp | Production of phosphate glass having good transmission in short-wave region |
| JPS60235740A (en) * | 1984-04-18 | 1985-11-22 | シヨツト グラスヴエルケ | Glass for optical colored filter |
| JPH01286935A (en) * | 1988-05-12 | 1989-11-17 | Minolta Camera Co Ltd | Ultraviolet transmission glass |
| JPH0393647A (en) * | 1989-09-01 | 1991-04-18 | Minolta Camera Co Ltd | Ultraviolet ray transmitting glass |
| JPH0455337A (en) * | 1990-06-21 | 1992-02-24 | Ohara Inc | Ultraviolet ray transmitting glass |
| JPH06107428A (en) * | 1990-10-05 | 1994-04-19 | Carl Zeiss:Fa | Alumphosphate glass containing copper oxide ii |
| JPH11268927A (en) * | 1998-03-20 | 1999-10-05 | Hoya Corp | Phosphate glass for precision molding, optical element using the same, and production of optical element |
| JP2002055201A (en) * | 2000-08-11 | 2002-02-20 | Hoya Corp | Optical recording reproducing optical system and optical information recording and reproducing device |
| JP2002211951A (en) * | 2001-01-11 | 2002-07-31 | Okamoto Glass Co Ltd | Infrared ray-shielding green glass |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018188353A (en) * | 2017-04-28 | 2018-11-29 | ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ | Filter glass |
| US10703669B2 (en) | 2017-04-28 | 2020-07-07 | Schott Ag | Filter gas |
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