CN111448169A - Method for producing near-infrared-absorbing glass - Google Patents
Method for producing near-infrared-absorbing glass Download PDFInfo
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- CN111448169A CN111448169A CN201980006319.6A CN201980006319A CN111448169A CN 111448169 A CN111448169 A CN 111448169A CN 201980006319 A CN201980006319 A CN 201980006319A CN 111448169 A CN111448169 A CN 111448169A
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- 239000011521 glass Substances 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000006060 molten glass Substances 0.000 claims abstract description 26
- 239000002250 absorbent Substances 0.000 claims abstract description 9
- 230000002745 absorbent Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002834 transmittance Methods 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract 1
- 230000003595 spectral effect Effects 0.000 description 19
- 239000010949 copper Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 238000004017 vitrification Methods 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 238000004031 devitrification Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03B5/173—Apparatus for changing the composition of the molten glass in glass furnaces, e.g. for colouring the molten glass
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Glass Compositions (AREA)
- Optical Filters (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
The invention provides a method for easily manufacturing a light-splitting material with excellent light-splitting characteristicsA method for producing a near-infrared absorbing glass. The method for producing the near-infrared absorbing glass is characterized in that the glass contains 10-70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2A method for producing a near-infrared absorbent glass containing O (wherein R is at least 1 selected from the group consisting of L i, Na and K), wherein raw materials are heated and melted to form a molten glass, and the molten glass is bubbled with an oxidizing gas while being maintained at 1000 ℃ or lower.
Description
Technical Field
The present invention relates to a method for producing a near-infrared-absorbing glass capable of selectively absorbing near-infrared rays.
Background
In general, near infrared absorbing glass is used for the purpose of correcting the brightness of a solid-state image sensor such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) in a camera portion of an optical device such as a digital camera or a smartphone. In order to satisfy the spectral characteristics required for a near-infrared absorbing glass, a phosphate glass containing Cu is generally used. Near-infrared absorbing glass is also required to have chemical durability and weather resistance from a practical viewpoint, and therefore, various improvements have been made in composition and manufacturing method.
In order to improve chemical durability and weather resistance of phosphoric acid glass, it is proposed to contain SiO for reinforcing the glass skeleton2、Al2O3The above (see, for example, patent document 1). However, in this case, the meltability tends to decrease and the melting temperature tends to increase. Shows absorbed Cu in the near infrared region when the melting temperature rises2+The ions are reduced to produce Cu which shows absorption in the ultraviolet region+Since the transmittance of ions in the ultraviolet to visible light ranges is likely to decrease, it is difficult to obtain desired spectral characteristics.
Therefore, in order to maintain the oxidation state of copper, a method of adding an oxidizing agent to the raw material is proposed.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-
Disclosure of Invention
Technical problem to be solved by the invention
However, the addition of the oxidizing agent itself may adversely affect the spectroscopic characteristics.
In view of the above, an object of the present invention is to provide a method for easily producing a near-infrared absorbing glass having excellent spectral characteristics.
Technical solution for solving technical problem
The method for producing a near-infrared-absorbing glass of the present invention is characterized in that the glass contains 10 to 70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2A method for producing a near-infrared absorbent glass containing O (wherein R is at least 1 selected from the group consisting of L i, Na, and K), wherein a raw material is heated and melted to form a molten glass, and the molten glass is kept at 1000 ℃ or lower while being bubbled with an oxidizing gas, whereby the molten glass is easily oxidized by keeping the molten glass at a low temperature of 1000 ℃ or lower+Change of valence into Cu2+Can obtain Cu+A small amount of glass and has excellent spectral characteristics.
In the method for producing a near-infrared-absorbing glass of the present invention, the near-infrared-absorbing glass preferably contains 20 to 60% by mass of P2O55 to 35% of CuO, and more than 0 and 40% or less of R2O (wherein, R is at least 1 selected from L i, Na and K), 0-19% of Al2O30 to 50% of R 'O (wherein R' is at least 1 selected from Mg, Ca, Sr and Ba).
The near infrared ray absorbing glass of the present invention is characterized by containing 10 to 70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2O (wherein R is at least 1 selected from the group consisting of L i, Na and K), a thickness of less than 0.2mm, and a light transmittance at a wavelength of 500nm of 82% or more at a thickness of 0.05mm the near infrared ray absorption glass of the present invention contains 3% by mass or more of CuO, and therefore, even when the thickness is as thin as less than 0.2mm, the glass can be used as a near infrared ray absorption glassExcellent spectral characteristics can be obtained. In addition, since the thickness is as thin as less than 0.2mm, the optical device can be easily thinned.
The near-infrared ray absorbing glass of the present invention preferably has a light transmittance of 50% or less for light having a wavelength of 800nm at a thickness of 0.05 mm.
The near infrared ray absorbing glass of the present invention is characterized by containing 10 to 70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2O (wherein R is at least 1 selected from the group consisting of L i, Na and K) and a dissolved oxygen amount of 100 mu L/g or more, and the near-infrared-absorbing glass of the present invention is sufficiently oxidized in such an amount that the dissolved oxygen amount is 100 mu L/g or more, and therefore, Cu contained in the glass+The amount of (A) is small, and excellent spectral characteristics are easily obtained. The "dissolved oxygen amount" refers to the amount of oxygen released from the glass when the glass is heated from 450 ℃ to 1450 ℃ at a temperature increase rate of 8 ℃/min in an inert atmosphere such as helium.
The near-infrared absorbing glass of the present invention is characterized by containing 3 to 40% by mass of CuO, and having a light transmittance of 82% or more for light having a wavelength of 500nm and a light transmittance of 50% or less for light having a wavelength of 800nm at a thickness of 0.05 mm.
ADVANTAGEOUS EFFECTS OF INVENTION
The near-infrared-absorbing glass having excellent spectral characteristics can be easily produced by the production method of the present invention.
Detailed Description
The method for producing the near-infrared-absorbing glass of the present invention will be explained.
First, a glass raw material blended so as to have a desired composition is heated and melted to obtain molten glass. The melting temperature is preferably 500 to 1200 ℃, 550 to 1100 ℃, particularly 600 to 1000 ℃. When the melting temperature is too low, it is difficult to obtain homogeneous glass. On the other hand, when the melting temperature is too high, the molten glass is reduced, and Cu+Too much amount of Cu, so that it is difficult to blow Cu even if the temperature is kept at 1000 ℃ or lower and the oxidizing gas is blown+The amount of (A) is sufficiently small. As a result, it is difficult to obtain desired spectral characteristics.
The obtained molten glass was kept at a certain temperature. The holding temperature is preferably 1000 ℃ or lower, 950 ℃ or lower, particularly 900 ℃ or lower. When the holding temperature is too high, Cu+Can not be oxidized into Cu sufficiently2+It is difficult to obtain desired spectral characteristics. Further, when the holding temperature is too low, devitrification is likely to occur during holding of the molten glass or at the time of molding, and therefore, the lower limit of the holding temperature is preferably 500 ℃ or more, 550 ℃ or more, particularly 600 ℃ or more. The holding time of the molten glass at the holding temperature is preferably 1 to 20 hours, particularly 3 to 18 hours. Too short of a holding time, Cu+Can not be oxidized into Cu sufficiently2+It is difficult to obtain desired spectral characteristics. On the other hand, if the holding time is too long, the glass component volatilizes, and it is difficult to obtain a desired composition. As a result, the spectral characteristics and the like may be adversely affected.
Further, when the molten glass is held at the holding temperature, the oxidizing gas is blown into the molten glass. Thus, the molten glass becomes easily oxidized, and therefore, Cu+The amount of (A) is reduced, and excellent spectral characteristics are easily obtained. Further, examples of the oxidizing gas include oxygen, ozone, and nitrogen oxides (dinitrogen monoxide, nitrogen dioxide, and the like). Oxygen is particularly preferable in view of cost, environmental aspects, and safety aspects.
The molten glass held for a certain period of time is then formed into a desired shape. Examples of the molding method include a casting method, a down-draw (down-draw) method, and a roll-out (roll-out) method. The formed glass can be subjected to post-processing such as cutting, grinding and the like as required to obtain the near infrared ray absorption glass.
Next, the near-infrared absorbing glass of the present invention will be explained.
The near infrared ray absorbing glass of the present invention contains 10 to 70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2O (wherein R is at least 1 selected from L i, Na and K.) the reason why the glass composition is thus specified is explained below.
P2O5An essential component for forming a glass skeleton. P2O5The content of (B) is preferably 10 to 70%, 20 to 60%, 31 to 56%, 41 to 50%, particularly 45 to 49%. P2O5When the content of (b) is too small, vitrification becomes difficult, and it becomes difficult to obtain desired spectral characteristics. Specifically, the near infrared ray absorption characteristics are liable to be degraded. On the other hand, P2O5When the content of (b) is too large, the weather resistance tends to be lowered.
CuO is an essential component for absorbing near infrared rays. The content of CuO is preferably 3 to 40%, 4 to 37%, 5 to 35%, particularly 6 to 30%. When the content of CuO is too small, the glass needs to be thickened in order to obtain desired near infrared absorption characteristics, and as a result, it is difficult to make the optical device thin. On the other hand, when the content of CuO is too large, the liquidus temperature becomes high, and the devitrification resistance is liable to decrease.
R2O (wherein R is at least 1 selected from L i, Na and K) is a component for lowering melting temperature R2The content of O is preferably more than 0 and 50% or less, more than 0 and 40% or less, 3 to 30%, particularly 5 to 20%. R2When the O content is too small, the melting temperature becomes high, and it becomes difficult to blow Cu even if the temperature is maintained at 1000 ℃ or lower and the oxidizing gas is blown+The amount of (A) is sufficiently small. As a result, it is difficult to obtain desired spectral characteristics. In another aspect, R2When the content of O is too large, vitrification becomes difficult.
In addition, R2Preferred ranges of the respective components of O are described below L i2The content of O is preferably 0 to 50%, more than 0 and 40% or less, 3 to 30%, particularly 5 to 20%. Na (Na)2The content of O is preferably 0 to 50%, more than 0 and 40% or less, 3 to 30%, particularly 5 to 20%. K2The content of O is preferably more than 0 and 50% or less, more than 0 and 40% or less, 3 to 30%, particularly 5 to 20%.
The near-infrared absorbent glass of the present invention may contain the following components in addition to the above components.
Al2O3Is a component for greatly improving weather resistance. In addition, the first and second substrates are,it is also a component for improving resistance to devitrification. Al (Al)2O3The content of (b) is preferably 0 to 19%, 3 to 14%, 3 to 8%, particularly 4 to 6%. Al (Al)2O3When the content of (b) is too large, the meltability tends to decrease and the melting temperature tends to increase.
R 'O (wherein R' is at least 1 selected from the group consisting of Mg, Ca, Sr and Ba) is a component that improves weather resistance and improves meltability. In addition, the composition also improves resistance to devitrification. 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 derived from the R' O component are likely to precipitate during molding.
Preferred ranges of the contents of the respective components of R' O are as follows.
MgO is a component for improving weather resistance. The content of MgO is preferably 0 to 15%, particularly 0.4 to 7%. When the content of MgO is too large, vitrification becomes difficult.
CaO is a component for improving weather resistance, similarly to MgO. The preferable content of CaO is 0 to 15%, particularly 0.4 to 7%. When the content of CaO is too large, vitrification becomes difficult.
Like MgO, SrO is a component for improving weather resistance. The content of SrO is preferably 0 to 12%, particularly 0.3 to 5%. When the SrO content is too large, vitrification becomes difficult.
BaO is a component for improving the stability of vitrification and improving weather resistance. Especially in P2O5In a small amount, the effect of glass transition stability by BaO is easily obtained. The content of BaO is preferably 0 to 30%, 5 to 30%, 7 to 25%, particularly 7.2 to 23%. When the content of BaO is too large, crystals derived from BaO are likely to precipitate during molding.
The near-infrared absorbing glass of the present invention contains CuO in an amount of 3% or more. When the content of CuO is increased, devitrification becomes easy, but Al can be contained2O3R' O to improve resistance to devitrification.
ZnO is a component for improving the stability of vitrification and weather resistance. The content of ZnO is preferably 0 to 13%, 0.1 to 12%, particularly 1 to 10%. When the content of ZnO is too large, the meltability is lowered and the film is meltedThe temperature becomes high, and as a result, it becomes difficult to obtain desired spectral characteristics. In addition, crystals derived from the ZnO component are likely to precipitate. In addition, especially in P2O5In a small amount, the effect of glass transition stability by ZnO can be easily obtained.
Nb2O5And Ta2O5A component for improving weather resistance. Nb2O5And Ta2O5The content of each component (A) is preferably 0 to 20%, 0.1 to 20%, 1 to 18%, particularly 2 to 15%. When the content of these components is too large, the melting temperature becomes high, and it becomes difficult to obtain desired spectral characteristics. In addition, Nb2O5And Ta2O5The total amount of (A) is preferably 0 to 20%, 0.1 to 20%, 1 to 18%, particularly 2 to 15%.
GeO2A component for improving weather resistance. GeO2The content of (B) is preferably 0 to 20%, 0.1 to 20%, 0.3 to 17%, particularly 0.4 to 15%. GeO2When the content of (b) is too large, the melting temperature becomes high, and it becomes difficult to obtain desired spectral characteristics.
SiO2Is a component for strengthening the glass skeleton. In addition, it has an effect of improving weather resistance. SiO 22The content of (B) is preferably 0 to 10%, 0.1 to 8%, particularly 1 to 6%. SiO 22When the content of (b) is too large, the weather resistance tends to be deteriorated. In addition, there is a tendency that vitrification becomes unstable.
In addition to the above components, B may be contained within a range not impairing the effects of the present invention2O3、Y2O3、La2O3、CeO2、Sb2O3And the like. Specifically, the content of each of these components is preferably 0 to 3%, particularly preferably 0 to 2%. Further, although chemical durability can be improved by containing fluorine, fluorine is an environmental load substance, and is preferably contained in an anion% of 15% or less, 10% or less, 5% or less, and 1% or less, and particularly preferably not contained.
The near-infrared-absorbing glass of the present invention preferably has a liquidus temperature of 900 ℃ or lower, 890 ℃ or lower, 880 ℃ or lower, 870 ℃ or lower, 860 ℃ or lower, particularly 850 ℃ or lower. If the liquid phase temperature is too high, devitrification is likely to occur in the production process (particularly, at the time of molding).
The near-infrared absorbent glass obtained by the above method can achieve both high transmittance in the visible light range and excellent light absorption characteristics in the near-infrared range. Specifically, the light transmittance of light having a wavelength of 500nm at a thickness of 0.05mm is preferably 82% or more, 83% or more, 84% or more, 85% or more, 86% or more, 87% or more, and particularly preferably 88% or more. On the other hand, the light transmittance at a wavelength of 800nm is preferably 50% or less, 40% or less, 35% or less, 30% or less, 29% or less, 28% or less, 27% or less, particularly preferably 26.5% or less, and the light transmittance at a wavelength of 1200nm is preferably 70% or less, 65% or less, 60% or less, 59% or less, 58% or less, 57% or less, 56% or less, particularly preferably 55% or less.
The near-infrared absorbing glass of the present invention is generally used in a plate shape. The thickness is less than 0.2mm, preferably 0.18mm or less, 0.15mm or less, 0.12mm or less, 0.1mm or less, thinner than 0.1mm, 0.07mm or less, and particularly preferably 0.05mm or less. If the thickness is too large, the optical device tends to be difficult to be thin. From the viewpoint of mechanical strength, the lower limit of the thickness is preferably 0.01mm or more.
The near-infrared ray-absorbing glass of the present invention has a dissolved oxygen amount of 100 μ L/g or more, preferably 500 μ L/g or more, 1000 μ L0/g or more, 1500 μ L/g or more, 2000 μ L/g or more, 2500 μ L/g or more, 3000 μ L/g or more, 3100 μ L/g or more, 3200 μ L/g or more, 3300 μ L/g or more, and particularly preferably 3400 μ L/g or more, and when the dissolved oxygen amount is too small, the glass is not sufficiently oxidized, and therefore, Cu contained in the glass is not oxidized sufficiently, and when the dissolved oxygen amount is too small, Cu contained in the glass is not oxidized sufficiently+The amount of the above-mentioned component (B) is large, and it is difficult to obtain desired spectral characteristics, and the upper limit of the amount of the dissolved oxygen is not particularly limited, and is actually 100000. mu. L/g or less.
Examples
The method for producing the near-infrared-absorbing glass of the present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
(example 1)
46.0% by mass of P2O56.9% of CuO and 13.9% of K2O, 6.6% Al2O3The near infrared ray absorbing glass obtained was subjected to mirror polishing on both sides so as to have a thickness of 0.05mm, and the light transmittance was measured at a wavelength of 300 to 1300nm by a spectrophotometer (UV-3100 PC manufactured by Shimadzu CORPORATION) showing good spectral characteristics such as 89% at a wavelength of 500nm, 26% at a wavelength of 800nm and 52% at a wavelength of 1200nm, and the obtained near infrared ray absorbing glass was subjected to temperature rise and desorption gas analyzer (CAANE L), and the temperature rise and desorption of oxygen was measured at a temperature rise and desorption rate of 358 ℃ from a temperature rise and desorption/or pyrolysis of oxygen in a pyrolysis gas analyzer (CAANE L) at a temperature rise and desorption rate of oxygen of 3308 μ C/450 μ C, and the temperature rise and desorption rate of oxygen is measured at a temperature rise and desorption rate of 3308 μ C/1450 μ C, wherein the molten glass was maintained at 900 ℃ for 5 hours while bubbling oxygen into the molten glass.
(example 2)
A near-infrared absorbent glass was obtained in the same manner as in example 1, except that the holding temperature of the molten glass during oxygen bubbling into the molten glass was changed to 950 ℃ and the holding time was changed to 6 hours, and the obtained near-infrared absorbent glass had a light transmittance of 88% at a wavelength of 500nm, a light transmittance of 26% at a wavelength of 800nm, a light transmittance of 53% at a wavelength of 1200nm, and a dissolved oxygen content of 3100. mu. L/g.
(example 3)
A near-infrared absorbent glass was obtained in the same manner as in example 1, except that the holding temperature of the molten glass during bubbling with oxygen into the molten glass was changed to 880 ℃ and the holding time was changed to 8 hours, and the obtained near-infrared absorbent glass had a light transmittance of 90% at a wavelength of 500nm, a light transmittance of 25% at a wavelength of 800nm, a light transmittance of 52% at a wavelength of 1200nm, and a dissolved oxygen content of 3400. mu. L/g.
(examples 4 to 52)
A near-infrared ray transmitting glass was produced and the light transmittance and the amount of dissolved oxygen were measured in the same manner as in example 1, except that the composition was changed as shown in tables 1 to 5. The results are shown in tables 1 to 5.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
As is clear from tables 1 to 5, in examples 4 to 52, the light transmittance at a wavelength of 500nm is 85 to 90%, the light transmittance at a wavelength of 800nm is 19 to 31%, the light transmittance at a wavelength of 1200nm is 49 to 57%, and the dissolved oxygen content is 3000 to 3500. mu. L/g.
Comparative example
P was 62.1% by mass2O57.6 percent of CuO and 3.8 percent of Al2O3Raw material powders prepared in such a manner as to have a composition of 3.1% MgO, 2.9% CaO and 20.5% BaO were put into a cylindrical platinum crucible, and were heated and melted at 1100 ℃ for 2 hours to form homogeneous molten glass. Then, the mixture was poured out onto a molten glass carbon plate, cooled and solidified, and then annealed. The obtained plate-like glass was made to have a thickness of 0.05mmBoth surfaces were mirror-polished, thereby obtaining a near-infrared absorbing glass. The near-infrared-absorbing glass thus obtained was measured for light transmittance in the wavelength range of 300 to 1300nm by a spectrophotometer (UV-3100 PC, Shimadzu corporation). 76% at a wavelength of 500nm, 52% at a wavelength of 800nm and 72% at a wavelength of 1200 nm.
As is clear from the above, examples 1 to 52 have higher light transmittance in the visible light range than comparative examples, and also clearly (sharp) cut off near infrared light.
Claims (6)
1. A method for producing a near-infrared-absorbing glass, characterized in that:
which contains 10 to 70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2A process for producing O near-infrared absorbent glass, wherein R is at least 1 member selected from the group consisting of L i, Na and K,
in the manufacturing method of the present invention, the substrate is,
heating and melting the raw materials to form molten glass,
bubbling the molten glass with an oxidizing gas while maintaining the molten glass at 1000 ℃ or lower.
2. The method for producing a near-infrared-absorbing glass according to claim 1, wherein:
the near infrared ray absorbing glass contains 20-60% by mass of P2O55 to 35% of CuO, and more than 0 and 40% or less of R2O, 0-19% Al2O3And 0-50% of R 'O, wherein R is at least 1 selected from L i, Na and K, and R' is at least 1 selected from Mg, Ca, Sr and Ba.
3. A near-infrared ray absorption glass characterized in that:
10 to 70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2O, wherein R is at least 1 selected from L i, Na and K,
the thickness is less than 0.2mm,
the light transmittance of light having a wavelength of 500nm is 82% or more at a thickness of 0.05 mm.
4. The near-infrared ray absorption glass according to claim 3, wherein:
the light transmittance of light having a wavelength of 800nm is 50% or less at a thickness of 0.05 mm.
5. A near-infrared ray absorption glass characterized in that:
10 to 70% by mass of P2O53 to 40% of CuO, and more than 0 and not more than 50% of R2O, wherein R is at least 1 selected from L i, Na and K,
the dissolved oxygen content is more than 100 mu L/g.
6. A near-infrared ray absorption glass characterized in that:
contains 3 to 40 mass% of CuO,
when the thickness is 0.05mm, the light transmittance of light with the wavelength of 500nm is more than 82%, and the light transmittance of light with the wavelength of 800nm is less than 50%.
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| JP2018038675 | 2018-03-05 | ||
| JP2018-038675 | 2018-03-05 | ||
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| JP2018-146501 | 2018-08-03 | ||
| JP2018-227930 | 2018-12-05 | ||
| JP2018227930A JP7138849B2 (en) | 2018-03-05 | 2018-12-05 | Manufacturing method of near-infrared absorbing glass |
| PCT/JP2019/003771 WO2019171851A1 (en) | 2018-03-05 | 2019-02-04 | Method of manufacturing near infrared ray absorbing glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040082460A1 (en) * | 2002-07-05 | 2004-04-29 | Hoya Corporation | Near-infrared light-absorbing glass, near-infrared light-absorbing element, near-infrared light-absorbing filter, and method of manufacturing near-infrared light-absorbing formed glass article, and copper-containing glass |
| CN102653450A (en) * | 2010-12-23 | 2012-09-05 | 肖特公开股份有限公司 | Fluorophosphate glasses |
| CN103508670A (en) * | 2012-06-22 | 2014-01-15 | 肖特公开股份有限公司 | Coloured glasses |
| JP2015089855A (en) * | 2013-11-05 | 2015-05-11 | 日本電気硝子株式会社 | Near-infrared absorbing glass |
| WO2017208679A1 (en) * | 2016-06-01 | 2017-12-07 | 日本電気硝子株式会社 | Method and device for manufacturing near infrared absorbing glass |
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| JP4169545B2 (en) * | 2002-07-05 | 2008-10-22 | Ｈｏｙａ株式会社 | Near-infrared light absorbing glass, near-infrared light absorbing element, near-infrared light absorbing filter, and method for producing near-infrared light absorbing glass molded body |
| US20070099787A1 (en) * | 2005-04-22 | 2007-05-03 | Joseph Hayden | Aluminophosphate glass containing copper (II) oxide and uses thereof for light filtering |
| JP2009263190A (en) * | 2008-04-29 | 2009-11-12 | Ohara Inc | Infrared absorption glass |
| JP5609090B2 (en) * | 2009-12-08 | 2014-10-22 | 旭硝子株式会社 | Near-infrared cut filter glass |
| JP5609754B2 (en) * | 2011-04-18 | 2014-10-22 | 旭硝子株式会社 | Near-infrared cut filter glass |
| JP2017014044A (en) * | 2015-06-30 | 2017-01-19 | Hoya株式会社 | Near infrared absorbing glass and filter |
| DE102017207253B3 (en) * | 2017-04-28 | 2018-06-14 | Schott Ag | filter glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040082460A1 (en) * | 2002-07-05 | 2004-04-29 | Hoya Corporation | Near-infrared light-absorbing glass, near-infrared light-absorbing element, near-infrared light-absorbing filter, and method of manufacturing near-infrared light-absorbing formed glass article, and copper-containing glass |
| CN102653450A (en) * | 2010-12-23 | 2012-09-05 | 肖特公开股份有限公司 | Fluorophosphate glasses |
| CN103508670A (en) * | 2012-06-22 | 2014-01-15 | 肖特公开股份有限公司 | Coloured glasses |
| JP2015089855A (en) * | 2013-11-05 | 2015-05-11 | 日本電気硝子株式会社 | Near-infrared absorbing glass |
| WO2017208679A1 (en) * | 2016-06-01 | 2017-12-07 | 日本電気硝子株式会社 | Method and device for manufacturing near infrared absorbing glass |
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| KR20200130228A (en) | 2020-11-18 |
| JP7138849B2 (en) | 2022-09-20 |
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