WO2009084619A1 - モールド成型用赤外線透過ガラス - Google Patents
モールド成型用赤外線透過ガラス Download PDFInfo
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- WO2009084619A1 WO2009084619A1 PCT/JP2008/073695 JP2008073695W WO2009084619A1 WO 2009084619 A1 WO2009084619 A1 WO 2009084619A1 JP 2008073695 W JP2008073695 W JP 2008073695W WO 2009084619 A1 WO2009084619 A1 WO 2009084619A1
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- WO
- WIPO (PCT)
- Prior art keywords
- glass
- molding
- infrared
- infrared transmitting
- transmitting glass
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 51
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims description 39
- 239000005387 chalcogenide glass Substances 0.000 abstract description 12
- 230000003287 optical effect Effects 0.000 description 10
- 239000003708 ampul Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- 229910005866 GeSe Inorganic materials 0.000 description 1
- 229910005900 GeTe Inorganic materials 0.000 description 1
- 229910005642 SnTe Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
-
- 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
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
Definitions
- the present invention relates to an infrared transmitting glass for molding.
- Infrared light is mainly used in sensors used for crime prevention and authentication equipment. Therefore, the optical elements used in these sensors are made of an infrared transmitting material that transmits infrared light.
- these devices are also required to have high performance, small size, and high versatility. Therefore, it is necessary to reduce the size of sensors used in these devices, and the optical elements have high performance and small size, and high productivity is required in the manufacturing process.
- Examples of the infrared transmitting material include germanium and zinc selenide.
- these infrared transmitting materials are crystals, the processing means is limited to polishing molding. Therefore, it is difficult to mass-produce optical elements with complicated shapes such as lens arrays using these materials.
- germanium is expensive, it is not easy to use it for a versatile sensor or the like.
- Chalcogenide glasses are described in, for example, Patent Documents 1 to 5.
- Patent Document 1 describes the production of an optical element by a method of molding plastic using chalcogenide glass as a raw material and a glass composition suitable for it.
- Patent Documents 2 and 3 disclose the composition of chalcogenide glass. However, neither document describes a glass composition suitable for molding.
- Patent Documents 4 and 5 describe a method of molding chalcogenide glass. However, the specific composition of the chalcogenide glass is not described, and glass that is difficult to mold is included, and further study is necessary to improve the moldability.
- the main object of the present invention is to provide an infrared transmitting glass that is chalcogenide glass and is more suitable for molding than conventional products.
- the present invention relates to the following infrared transmitting glass for molding.
- 1. At a molar concentration, Ge: 2 to 22%, at least one selected from the group consisting of Sb and Bi: 6 to 34%, at least one selected from the group consisting of Sn and Zn: 1 to 20%, S Infrared transparent glass for molding containing at least one selected from the group consisting of Se and Te: 58 to 70%.
- Item 2. The infrared-transmitting glass for molding according to Item 1, wherein the yield point is 240 to 400 ° C. 3.
- Item 2. The infrared-transmitting glass for molding according to Item 1, wherein the expansion coefficient is 100 ⁇ 10 ⁇ 7 to 200 ⁇ 10 ⁇ 7 . 4).
- Item 2. The infrared-transmitting glass for molding according to Item 1, for producing a spherical lens, an aspherical lens, a lens array, a microlens array, or a diffraction grating by
- the infrared-transmitting glass for molding of the present invention is a chalcogenide glass, and at a molar concentration, Ge: 2 to 22%, at least one selected from the group consisting of Sb and Bi: 6 to 34%, Sn and Zn At least one selected from the group consisting of: 1 to 20%, and at least one selected from the group consisting of S, Se and Te: 58 to 70%.
- the infrared-transmitting glass for molding of the present invention having the above composition has high moldability as compared with conventional chalcogenide glass. Therefore, by using the infrared-transmitting glass for molding of the present invention, an optical element having infrared transparency can be easily produced by molding even if the optical element has a complicated shape.
- each component of the infrared transmitting glass for molding of the present invention will be described.
- each component influences each other to determine the specific properties of the glass material, so it is not always appropriate to discuss the quantitative range of each component according to the properties of each component, Below, the basis which prescribed
- the infrared transmitting glass for molding of the present invention is a molar concentration, Ge: 2-22%, At least one selected from the group consisting of Sb and Bi: 6-34%, At least one selected from the group consisting of Sn and Zn: 1 to 20%, At least one selected from the group consisting of S, Se and Te: 58 to 70%.
- Ge has a role of forming a glass skeleton structure.
- the content may be 2 to 22% in terms of molar concentration, but is preferably 3 to 22%. If the content is less than 2% or exceeds 22%, crystallization may occur.
- At least one selected from the group consisting of Sb and Bi has a role of forming a glass skeleton structure.
- the content may be 6 to 34% in terms of molar concentration, but is preferably 8 to 34%. If the content is less than 6% or exceeds 34%, crystallization may occur.
- At least one selected from the group consisting of Sn and Zn has a role of facilitating the formation of glass.
- the content may be 1 to 20% in terms of molar concentration, but is preferably 2 to 19%. If the content is less than 1% or exceeds 20%, crystallization may occur.
- At least one selected from the group consisting of S, Se, and Te has a role of forming a glass skeleton structure.
- the content may be 58 to 70% in terms of molar concentration, but is preferably 59 to 65%. If the content is less than 58%, crystallization may occur. If the content exceeds 70%, moldability may be reduced.
- the infrared transmitting glass for molding of the present invention may contain P, Ga, In and the like in addition to the above components.
- the content (total amount) of these components is not limited, but is preferably 0 to 7%, more preferably 1 to 5%.
- the reason for adding these elements is not limited, for example, they are added for the purpose of easily forming glass.
- the infrared transmission performance of the infrared transmission glass for molding of the present invention can be appropriately set according to the final product.
- the average transmittance of infrared rays having a wavelength of 2 to 10 ⁇ m is about 50 to 70%.
- the yield point is preferably about 240 to 400 ° C, more preferably 250 to 390 ° C. If the yield point is less than 240 ° C, the glass may crystallize during molding. Moreover, when a yield point exceeds 400 degreeC, there exists a possibility that a mold and glass may react.
- the expansion coefficient is preferably 100 ⁇ 10 ⁇ 7 to 200 ⁇ 10 ⁇ 7, and more preferably 105 ⁇ 10 ⁇ 7 to 170 ⁇ 10 ⁇ 7 .
- the expansion coefficient is less than 100 ⁇ 10 ⁇ 7 or exceeds 200 ⁇ 10 ⁇ 7 , molding may be difficult.
- the method for producing the infrared-transmitting glass for molding of the present invention is not limited. For example, it can be produced by enclosing a predetermined amount of each ingredient in a quartz ampule and vitrifying the contents by heat treatment.
- the raw material is a single metal such as Ge, Sb, Bi, Sn, Zn, S, Se, Te, or GeS 2 , GeSe 2 , GeTe 2 , Sb 2 S 3 , Sb 2 Se 3 , Sb 2 Te 3 , Bi. 2 S 3, Bi 2 Se 3 , BiTe 3, SnS, SnSe, SnTe, ZnS, ZnSe, chalcogenide such as ZnTe can be used.
- the quartz ampoule to be used is sufficiently dried inside by a vacuum dryer. Further, during vitrification, heating at 500 to 1000 ° C. is preferable, and heating at 600 to 800 ° C. is more preferable.
- the heat treatment time may be a time during which the contents are sufficiently vitrified, but generally 3 to 30 hours are preferable, and 6 to 24 hours are more preferable.
- the infrared transmitting glass for molding of the present invention has high moldability.
- the glass is heated to near the softening point, and is molded into a desired shape by, for example, sandwiching between the upper mold and the lower mold and hot pressing.
- the heating temperature required for molding is not limited, but is preferably about 10 to 70 ° C. higher than the yield point, more preferably about 20 to 50 ° C. higher than the yield point.
- the optical element produced by molding is not limited, and examples thereof include an aspheric lens, a lens array, a microlens array, a diffraction grating, and the like that are required to transmit infrared rays. These are useful as optical elements used in various sensors using infrared rays.
- the infrared transmitting glass for molding of the present invention has higher moldability than conventional chalcogenide glass. Therefore, by using the infrared-transmitting glass for molding of the present invention, an optical element having infrared transparency can be easily produced by molding even if the optical element has a complicated shape.
- FIG. 2 is an X-ray diffraction pattern of infrared transmission glass produced in Example 1 and Comparative Example 1.
- FIG. 2 is an infrared transmittance curve of the infrared transmitting glass produced in Example 1.
- FIG. 2 is an upper surface photographed image of an aspheric glass lens produced from the glass sample of Example 1.
- Examples 1 to 10 and Comparative Examples 1 to 3 (Production of infrared transmitting glass for molding) A quartz ampule was prepared, and the inside was washed with purified water. Next, the rotary vacuum pump was operated and the quartz ampule was heated with a burner under vacuum to evaporate water. Next, each component was mixed so as to have the composition shown in Table 1 below and placed in the quartz ampoule, and the ampoule inside was sufficiently evacuated with a rotary vacuum pump, and then sealed with a H 2 —O 2 burner. Tubed.
- the sealed quartz ampule was heated to 750 ° C. at a rate of temperature increase of 20 ° C./hour and then held at the same temperature for 12 hours. Next, the contents were naturally cooled to room temperature to vitrify the contents.
- vitrified contents of Examples 1 to 10 were heat-treated at 220 ° C. for 24 hours.
- the heat-treated contents (glass sample) were taken out from the ampule and optically polished.
- the yield point and expansion coefficient of the glass sample were measured using a thermomechanical analyzer (TMA-60 manufactured by Shimadzu Corporation).
- TMA-60 thermomechanical analyzer manufactured by Shimadzu Corporation.
- the yield point of the glass sample of Example 1 was 256 ° C.
- the expansion coefficient was 165 ⁇ 10 ⁇ 7 .
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
Description
1.モル濃度で、Ge:2~22%、Sb及びBiからなる群から選択される少なくとも1種:6~34%、Sn及びZnからなる群から選択される少なくとも1種:1~20%、S、Se及びTeからなる群から選択される少なくとも1種:58~70%を含有する、モールド成型用赤外線透過ガラス。
2.屈伏点が240~400℃である、上記項1に記載のモールド成型用赤外線透過ガラス。
3.膨張係数が100×10-7~200×10-7である、上記項1に記載のモールド成型用赤外線透過ガラス。
4.モールド成型により球面レンズ、非球面レンズ、レンズアレイ、マイクロレンズアレイ又は回折格子を作製するための、上記項1に記載のモールド成型用赤外線透過ガラス。
Ge:2~22%、
Sb及びBiからなる群から選択される少なくとも1種:6~34%、
Sn及びZnからなる群から選択される少なくとも1種:1~20%、
S、Se及びTeからなる群から選択される少なくとも1種:58~70%、を含む。
(モールド成型用赤外線透過ガラスの作製)
石英アンプルを用意し、その内部を精製水で洗浄した。次に、ロータリー真空ポンプを作動させて真空下で石英アンプルをバーナーで熱して水分を蒸発させた。次に、下記表1に示される組成となるように各成分を混合して石英アンプル内部に入れ、ロータリー真空ポンプでアンプル内部を十分に真空にした後、H2-O2バーナーを用いて封管した。
実施例1~10のガラスサンプルを窒素雰囲気中270℃においてモールド成型をし、非球面レンズを作製した。その結果、良好な非球面レンズが作製できた。
Claims (4)
- モル濃度で、Ge:2~22%、Sb及びBiからなる群から選択される少なくとも1種:6~34%、Sn及びZnからなる群から選択される少なくとも1種:1~20%、S、Se及びTeからなる群から選択される少なくとも1種:58~70%を含有する、モールド成型用赤外線透過ガラス。
- 屈伏点が240~400℃である、請求項1に記載のモールド成型用赤外線透過ガラス。
- 膨張係数が100×10-7~200×10-7である、請求項1に記載のモールド成型用赤外線透過ガラス。
- モールド成型により球面レンズ、非球面レンズ、レンズアレイ、マイクロレンズアレイ又は回折格子を作製するための、請求項1に記載のモールド成型用赤外線透過ガラス。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/744,171 US8603928B2 (en) | 2007-12-28 | 2008-12-26 | Infrared transmitting glass for mold forming |
EP08866641.7A EP2226304B1 (en) | 2007-12-28 | 2008-12-26 | Infrared transmitting glass suitable for mold forming |
CN2008801228944A CN101910080A (zh) | 2007-12-28 | 2008-12-26 | 用于模具成型的红外透射玻璃 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007-340306 | 2007-12-28 | ||
JP2007340306A JP5339720B2 (ja) | 2007-12-28 | 2007-12-28 | モールド成型用赤外線透過ガラス |
Publications (1)
Publication Number | Publication Date |
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WO2009084619A1 true WO2009084619A1 (ja) | 2009-07-09 |
Family
ID=40824332
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/073695 WO2009084619A1 (ja) | 2007-12-28 | 2008-12-26 | モールド成型用赤外線透過ガラス |
Country Status (6)
Country | Link |
---|---|
US (1) | US8603928B2 (ja) |
EP (1) | EP2226304B1 (ja) |
JP (1) | JP5339720B2 (ja) |
CN (1) | CN101910080A (ja) |
RU (1) | RU2010131442A (ja) |
WO (1) | WO2009084619A1 (ja) |
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WO2018016149A1 (ja) * | 2016-07-20 | 2018-01-25 | 日本電気硝子株式会社 | 赤外線透過性レンズの製造方法、赤外線透過性レンズ及び赤外線カメラ |
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- 2008-12-26 US US12/744,171 patent/US8603928B2/en active Active
- 2008-12-26 EP EP08866641.7A patent/EP2226304B1/en active Active
- 2008-12-26 RU RU2010131442/03A patent/RU2010131442A/ru unknown
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2015129072A (ja) * | 2014-01-09 | 2015-07-16 | 日本電気硝子株式会社 | 赤外線透過ガラス |
JP2017090904A (ja) * | 2015-11-09 | 2017-05-25 | 株式会社タムロン | 密着積層型回折光学素子 |
US10294144B2 (en) | 2015-11-20 | 2019-05-21 | AGC Inc. | Optical glass |
WO2018016149A1 (ja) * | 2016-07-20 | 2018-01-25 | 日本電気硝子株式会社 | 赤外線透過性レンズの製造方法、赤外線透過性レンズ及び赤外線カメラ |
US11155487B2 (en) | 2016-07-20 | 2021-10-26 | Nippon Electric Glass Co., Ltd. | Method for manufacturing infrared-transmissible lens, infrared-transmissible lens, and infrared camera |
Also Published As
Publication number | Publication date |
---|---|
CN101910080A (zh) | 2010-12-08 |
EP2226304B1 (en) | 2021-11-03 |
US8603928B2 (en) | 2013-12-10 |
EP2226304A1 (en) | 2010-09-08 |
RU2010131442A (ru) | 2012-02-10 |
JP5339720B2 (ja) | 2013-11-13 |
EP2226304A4 (en) | 2014-01-15 |
US20100285946A1 (en) | 2010-11-11 |
JP2009161374A (ja) | 2009-07-23 |
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