CN105906204A - Near-infrared absorption glass, element and light filter - Google Patents
Near-infrared absorption glass, element and light filter Download PDFInfo
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- CN105906204A CN105906204A CN201610239348.5A CN201610239348A CN105906204A CN 105906204 A CN105906204 A CN 105906204A CN 201610239348 A CN201610239348 A CN 201610239348A CN 105906204 A CN105906204 A CN 105906204A
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- 239000011521 glass Substances 0.000 title claims abstract description 117
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 64
- 238000002835 absorbance Methods 0.000 claims description 13
- 238000004031 devitrification Methods 0.000 abstract description 17
- 238000002834 transmittance Methods 0.000 abstract description 17
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 230000035945 sensitivity Effects 0.000 description 7
- 238000012937 correction Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000005304 optical glass Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005365 phosphate glass Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000740 envenomation Toxicity 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000146 host glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004554 molding of glass Methods 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- -1 oxide Chemical compound 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000009466 transformation Effects 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
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/226—Glass filters
Landscapes
- 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
The invention provides near-infrared absorption glass with excellent devitrification resistance and excellent transmission property within visible range, an element and a light filter. Expressed by cation and anion, the glass contains 15-35% of P<5+>, 5-20% of Al<3+>, 1-30% of Li<+>, 0-10% of Na<+>, 0-3% of K<+>, 0.1-8% of Cu<2+>, 0.1-10% of Mg<2+>, 1-20% of Ca<2+>, 15-35% of Sr<2+>, 10-30% of Ba<2+>, O<2-> and F<->. When thickness of the glass is 1mm, transmissivity is greater than 80% at the wavelength of 400 nm, and transmissivity is greater than 85% at the wavelength of 500 nm. For spectrum transmittance within the wavelength range of 500-700 nm, when transmittance is 50%, the corresponding wavelength range is 615+/-10 nm.
Description
The application is for Application No. 201210036856.5, filing date on February 17th, 2012, entitled " the reddest
Outer smooth heat absorbing glass, element and light filter " the divisional application of application for a patent for invention.
Technical field
The present invention relates to a kind of near-infrared absorption glass, near-infrared absorption element and near-infrared absorption filter
Device.In particular it relates to the near-infrared absorption light filter of a kind of applicable chromatic sensitivity correction is used, devitrification resistance property is excellent
Near-infrared absorption glass, and the near-infrared absorption element that is made up of this glass and light filter.
Background technology
In recent years, for the spectrum sensitivity of the semiconductor camera element such as CCD, CMOS of digital camera and VTR photographing unit
Degree, spreads to the near-infrared field started near 1100nm from visual field, and the light filter using absorption near-infrared field light can
To obtain being similar to the visual sense degree of people.Therefore, the demand of chromatic sensitivity correction light filter is increasing, and this is just to being used for manufacturing
The near-infrared absorption functional glass of this type of light filter is had higher requirement, and i.e. requires that this type of glass has at visible range excellent
Different through characteristic.
In prior art, near-infrared ray absorption glass is by adding Cu in phosphate glass or fluorphosphate glass2+
Manufacture near-infrared absorption glass.But relatively for fluorphosphate glass, phosphate glass chemical stability is poor, glass
If be exposed to for a long time hot and humid in the environment of, glass surface can produce be full of cracks and the defect of nebulousurine.
Summary of the invention
The technical problem to be solved is to provide a kind of has superior devitrification resistance and excellent thoroughly at visible range
Cross near-infrared absorption glass, element and the light filter of characteristic.
The present invention solves above-mentioned technical problem the technical scheme is that near-infrared absorption glass, and its component is by sun
Ion represents the P containing 15-35%5+；The Al of 5-20%3+；The Li of 1-30%+；The Na of 0-10%+；The K of 0-3%+；0.1-8%
Cu2+；The Mg of 0.1-10%2+；The Ca of 1-20%2+；The Sr of 15-35%2+；The Ba of 10-30%2+；Simultaneously containing useful anion
The O represented2-And F-。
Further, the P containing 20-30%5+；And/or the Al of 10-15%3+；And/or the Li of 1-20%+；And/or 0-
The Na of 5%+；And/or the Cu of 1.2-5%2+；And/or the Mg of 2-8%2+；And/or the Ca of 5-15%2+；And/or the Sr of 21-30%2 +；And/or the Ba of 15-30%2+。
Further, the P containing 21-25%5+；And/or the Li of 2-10%+；And/or the Na of 0.5-3%+；And/or 1.8-
The Cu of 3%2+；And/or the Mg of 3-7%2+；And/or the Ca of 7-11%2+；And/or the Sr of 23-28%2+；And/or 21-25%
Ba2+。
Further, R2+Content is 30-65%, described R2+Represent Mg2+、Ca2+、Sr2+And Ba2+Sum.
Further, R2+Content is 40-65%, described R2+Represent Mg2+、Ca2+、Sr2+And Ba2+Sum.
Further, R2+Content is 54-65%, described R2+Represent Mg2+、Ca2+、Sr2+And Ba2+Sum.
Further, R2+Content is 54-60%, described R2+Represent Mg2+、Ca2+、Sr2+And Ba2+Sum.
Further, F-Content is 45-60%；O2-Content is 40-55%.
Further, F-Content is 48-57%；O2-Content is 43-52%.
Further, F-Content is big 50% but less than or equal to 57%；O2-Content is more than or equal to 43% but to be less than
50%.
Further, F-Content is 51-55%；O2-Content is 45-49%.
Further, F-Content is 51-53%；O2-Content is 47-49%.
Further, when the thickness of glass is 1mm, show more than 80% in wavelength 400nm absorbance, at wavelength 500nm
Absorbance shows that the crystallize ceiling temperature of described near-infrared absorption glass is below 650 DEG C more than 85%.
Further, during described near-infrared absorption thickness of glass 1mm, show more than 88% in wavelength 400nm absorbance,
Show that the crystallize ceiling temperature of described near-infrared absorption glass is below 600 DEG C more than 90% in wavelength 500nm absorbance.
Near-infrared absorption element, is made up of above-mentioned near-infrared absorption glass.
Near-infrared absorption light filter, is made up of above-mentioned near-infrared absorption glass.
The invention has the beneficial effects as follows: the present invention is using fluophosphate glass as host glass, by controlling fluorophosphoric acid alkali
R in matter glass composition2+Content, while improving glass devitrification resistance, can strengthen the alkali content of vitreous humour, suppress Cu2+
It is reduced into Cu+So that the near-infrared absorption excellent performance of glass.When the thickness of glass of the present invention is 1mm, at wavelength 400nm
Absorbance shows more than 80%, shows more than 85% in wavelength 500nm absorbance, the light in the wave-length coverage of 500 to 700nm
In spectrum transmitance, the wavelength (λ that transmitance is corresponding when being 50%50Corresponding wavelength value) scope is the scope of 615 ± 10nm.
Accompanying drawing explanation
Fig. 1 is the spectral-transmission favtor curve chart of the near-infrared absorption glass of embodiments of the invention 1.
Detailed description of the invention
The near-infrared absorption glass of the present invention is based on fluophosphate glass, is added with near-infrared absorption effect
Cu2+And obtain.
Hereinafter, cationic components content accounts for the degree table of whole cation gross weight with this cation weight
Showing, the degree that anionic group content accounts for whole anion gross weight with this anion weight represents.
P5+For the basis of fluorphosphate glass, it it is a kind of important component producing absorption in region of ultra-red.When it
When content is less than 15%, glass near-infrared absorption effect reduces, and colour correction function deteriorates and band is green；More than 35% glass
Devitrification resistance all deteriorates with chemical stability, therefore P5+Content be defined to 15-35%, preferably 20-30%, more preferably
21-25%.
Al3+It it is glassy, a kind of component of chemical stability, resistance to sudden heating of one-tenth improving fluorphosphate glass.Work as Al3 +When content is less than 5%, do not reach the effect above；Work as Al3+When content is more than 20%, near-infrared absorbing characteristic reduces.Therefore,
Al3+Content is 5-20%, more preferably 10-15%.
Li+、Na+And K+It is to improve the meltability of glass, become the component of the transmitance of glassy and visible region.Relative to
Na+、K+For, a small amount of Li+Introduce more preferable to the chemical stability effect of glass.But work as Li+When content is more than 30%, glass
The chemical stability of glass and processing characteristics deteriorate.Therefore, Li+Content is 1-30%, preferably 1-20%, more preferably 2-
10%, most preferably 2-5%.
The present invention is preferably added to a small amount of Na+With Li+Consolute, can be effectively improved the chemical stability of glass.Na+Introducing
Also being improved the effect of meltbility and devitrification resistance, its content is 0-10%, preferably 0-5%, more preferably 0.5-3%.K+
Content is 0-3%, if its content is more than 3%, chemical durability of glass and processing characteristics reduce on the contrary.
R2+It is glassy, the devitrification resistance of one-tenth and the component of machinability, the R here being effectively improved glass2+Represent Mg2+、
Ca2+、Sr2+And Ba2+.As near-infrared absorption light filter, it is desirable to the light transmission rate being visible range is higher.Visual in order to improve
The transmitance in territory, the copper ion introduced in glass is not Cu+, it is necessary to it is Cu2+.If glass solution is in reducing condition, Cu2+Just
Become Cu+, its result is that the transmitance near wavelength 400nm will reduce.The present invention is by strengthening Mg in right amount2+、Ca2+、Sr2+With
Ba2+Total amount, add the alkali content of vitreous humour, it is possible to suppression Cu2+It is reduced into Cu+So that the near infrared light of glass is inhaled
Receive excellent performance.Mg2+、Ca2+、Sr2+And Ba2+If total amount less than 30%, devitrification resistance just has the tendency of deterioration,
If it exceeds 65%, also there is the tendency deteriorating devitrification resistance.Therefore, Mg2+、Ca2+、Sr2+And Ba2+Total amount is 30-
65%, preferably adding up to amount is 40-65%, and more preferably adding up to amount is more than 50% but less than or equal to 65%, enters one
Step preferably adds up to amount to be 54-65%, and most preferably adding up to content is 54-60%.
Wherein, Mg2+And Ca2+It is improved the effect of glass devitrification resistance, chemical stability, processability.Mg2+Amount is
0.1-10% is more satisfactory, more preferably 2-8%, further preferred 3-7%.Ca2+Content is preferably 1-20%, more preferably 5-
15%, the most preferably 7-11%.
Mg relatively2+And Ca2+For, the present invention has been primarily introduced into the Sr of high-load2+And Ba2+, it is being effectively increased R2+Contain
Amount, while bringing raising light transmission rate effect, Sr2+And Ba2+Also there is raising glass and become glassy, devitrification resistance, meltbility
Effect.Sr2+Content is preferably 15-35%, more preferably 21-30%, further preferred 23-28%.Same reason, Ba2+
Content is preferably 10-30%, more preferably 15-30%, more preferably 21-30%, most preferably 21-25%.
Copper in glass of the present invention is the leading indicator of near-infrared absorbing characteristic, and with Cu2+Exist.Work as Cu2+Content
During less than 0.1%, as near-infrared absorption light filter, it is impossible to sufficiently achieve necessary near-infrared absorption effect；But when it
When content is more than 8%, the devitrification resistance of glass, becomes glassy and all reduce.Therefore, Cu2+Content is 0.1-8%, preferably 1.2-
5%, more preferably 1.8-3%.
Containing the O as anion component in glass of the present invention2-And F-.In near-infrared ray absorption glass, molten when improving
When melting temperature, Cu2+Easily it is reduced to Cu+, the color of glass becomes green from blueness, thus compromises and colour sensitivity corrected
It is applied on quasiconductor image-forming component necessary characteristic.
F-It is to reduce the melt temperature of glass and improve the important anionic group of chemical stability.In the present invention, work as F-
When content is equal to or less than 45%, chemical stability reduces；Work as F-When content is more than 60%, because O2-Content reduces, Cu2+Subtract
Few can not get suppresses, and can produce Cu near 400nm2+The coloring caused.Therefore, F-Content is 45-60%, preferably 48-
57%, more preferably greater than 50% but less than or equal to 57%, more preferably 51-55%, more preferably 51-53%.
O2-Being a kind of important anionic group in glass of the present invention, its content is that total nonionic content deducts F-Rear surplus
Remaining whole content.Work as O2-Content very little time because Cu2+It is reduced to Cu+, so in short wavelength region, particularly existing
Absorption near 400nm becomes much larger until shown in green；But work as O2-Content too much time because the viscosity of glass becomes more
High thus cause higher melt temperature, so transmitance reduces.Therefore, O in the present invention2-Content be 40-55%, preferably model
Enclose for 43-52%, more preferably equal to or greater than 43% but less than 50%, more preferably 45-49%, most preferably 47-
49%.
The present invention is preferably by increasing F in right amount-Content, and F-Content is more than O2-Content, can be effectively reduced glass
Melt temperature, and increase F in right amount-The chemical stability that can also make glass is excellent, F--O2-Preferred scope be 0.1-
20%, further preferred scope is 0.1-10%, and most preferred range is 0.1-3%.
The present invention is by specific design of components, and light transmission rate is as follows:
When thickness of glass is 1mm, the spectral transmittance in the wave-length coverage of 400 to 1200nm has the spy being illustrated below
Property.
At the spectral transmittance of wavelength of 400nm more than or equal to 80%, preferably greater than or equal to 85%, more preferably greater than
Or equal to 88%.
At the spectral transmittance of wavelength of 500nm more than or equal to 85%, preferably greater than or equal to 88%, more preferably greater than
Or equal to 90%.
At the spectral transmittance of wavelength of 600nm more than or equal to 58%, preferably greater than or equal to 61%, more preferably greater than
Or equal to 64%.
At the spectral transmittance of wavelength of 700nm less than or equal to 12%, preferably lower than or equal to 10%, more preferably less than
Or equal to 9%.
At the spectral transmittance of wavelength of 800nm less than or equal to 5%, preferably lower than or equal to 3%, more preferably less than or
Equal to 2.5%, it is even more preferably less than or equal to 2%.
At the spectral transmittance of wavelength of 900nm less than or equal to 5%, preferably lower than or equal to 3%, more preferably less than or
Equal to 2.5%.
At the spectral transmittance of wavelength of 1000nm less than or equal to 7%, preferably lower than or equal to 6%, more preferably less than
Or equal to 5%.
At the spectral transmittance of wavelength of 1100nm less than or equal to 15%, preferably lower than or equal to 13%, the least
In or equal to 11%.
At the spectral transmittance of wavelength of 1200nm less than or equal to 24%, preferably lower than or equal to 22%, the least
In or equal to 21%.
That is, the absorption in the near infrared region wave-length coverage of 700nm to 1200nm is big, visible at 400nm to 600nm
Absorption in light region wavelength range is little.
In spectral transmittance in the wave-length coverage of 500 to 700nm, the wavelength (λ that transmitance is corresponding when being 50%50
Corresponding wavelength value) scope is 615 ± 10nm.
The transmitance of glass of the present invention refers to the value obtained in this way by spectrophotometer: assuming that glass sample has
Having parallel to each other and two planes of optical polish, light is vertical incidence from a parallel plane, from another one parallel plane
Outgoing, the intensity of this emergent light is exactly transmitance divided by the intensity of incident illumination, and this transmitance is also referred to as outer transmitance.
The above-mentioned characteristic of the glass according to the present invention, can realize quasiconductor image-forming component such as CCD or CMOS admirably
Color correction.
The near-infrared absorption glass of the present invention is in order in middle uses such as optical light filters, possess above-mentioned the most controlled
Transmission characteristics.But, if producing crystal in glass melting process, transmission characteristics can be produced baneful influence.Therefore,
Devitrification resistance is the key property that near-infrared absorption glass should possess.Devitrification resistance can be commented according to crystallize ceiling temperature
Valency, the crystallize ceiling temperature reducing glass just can improve the devitrification resistance of glass.If crystallize ceiling temperature uprises, then by
When melten glass is shaped to glass forming body, it is necessary to raising forming temperature is to avoid devitrification, and now, the molding of glass becomes tired
, in the melten glass become glass forming body, there is convection current, produce brush line in difficulty, or glass adhesion reduction during molding, or
Volatilization in person's glass becomes obvious, the envenomation of glass forming body, or volatile matter adheres on molded body, produces and pollutes
Problem.
Glass of the present invention has good transmission characteristics, and crystallize ceiling temperature can control below 680 DEG C simultaneously, excellent
Selected control system, below 650 DEG C, more preferably controls below 640 DEG C, and the range of choice of such condition of molding expands, and easily obtains simultaneously
Obtain near-infrared absorption glass well.
The crystallization property of above-mentioned glass uses temperature gradient furnace method to measure, specifically: glass is made the sample of 180*10*10mm
Product, side polishes, and takes out, examine under a microscope devitrification of glass situation after putting into the stove inside holding 4 hours with thermograde,
Glass occurs that the maximum temperature that crystal is corresponding is the crystallize ceiling temperature of glass.
Further, since the glass transformation temperature of near-infrared absorption glass of the present invention is below 358 DEG C, therefore, by essence
Close compressing after can be with the optical element of molded lens, diffraction grating etc..
Characteristic in terms of the chemical stability of glass is as follows: water-fast effect stability DW1 grade can be reached；Acidproof effect is steady
Qualitative DAReach 4 grades, preferably reach 3 grades, more preferably up to 2 grades.
Above-mentioned water-fast effect stability DW(powder method) presses the method for testing of GB/T17129, calculates according to following formula:
DW=(B-C)/(B-A) * 100
In formula: DWGlass leaches percent (%)
B filter and the quality (g) of sample
The quality (g) of sample after C filter and erosion
A filter quality (g)
By the leaching percent calculated, D is stablized in water-fast for optical glass effectWIt is divided into 6 classes see table.
| Classification | 1 | 2 | 3 | 4 | 5 | 6 |
| Leach percent (DW) | <0.04 | 0.04-0.10 | 0.10-0.25 | 0.25-0.60 | 0.60-1.10 | >1.10 |
Above-mentioned acidproof effect stability DA(powder method) presses the method for testing of GB/T17129, calculates according to following formula:
DA=(B-C)/(B-A) * 100
In formula: DAGlass leaches percent (%)
B filter and the quality (g) of sample
The quality (g) of sample after C filter and erosion
A filter quality (g)
By the leaching percent calculated, D is stablized in acidproof for optical glass effectAIt is divided into 6 classes see table.
| Classification | 1 | 2 | 3 | 4 | 5 | 6 |
| Leach percent (DA) | <0.20 | 0.20-0.35 | 0.35-0.65 | 0.65-1.20 | 1.20-2.20 | >2.20 |
The near-infrared absorption element that the present invention relates to is made up of described near-infrared absorption glass, can include
Laminal glass elements in near-infrared absorption light filter or lens etc., it is adaptable to the colour correction of solid-state imager
Purposes, possesses good transmission performance and chemical stability.
The near infrared filter device that the present invention relates to is the near-infrared absorption unit being made up of near-infrared absorption glass
Part, the most also possesses good optical transmittance property and chemical stability.
Embodiment
Hereinafter, reference example will be described in further detail the present invention.But, the invention is not restricted to described embodiment.
First, using fluoride, metaphosphate, oxide, nitrate and carbonate as frit, raw material is weighed and makes
It is to have the glass of the composition of display in Tables 1 and 2, after being thoroughly mixed, puts into mixing raw material with lid sealing
In platinum crucible, at a temperature of 700-900 DEG C, add heat fusing, after clarification uses oxygen protection homogenizing simultaneously, make melten glass
Flow continually out with constant flow rate from temperature control pipeline, after molding, obtain the optical glass of the present invention.
Embodiment 1-15 (the manufacture embodiment of near-infrared ray absorption glass)
Table 1
Table 2
R in table 1-22+For: Mg2+、Ca2+、Sr2+And Ba2+Total content.
Above-mentioned glass processing is become tabular, and two sides relative to each other is carried out optical polish is used for measuring with preparation
Cross the sample of rate, use spectral transmission instrument to measure the spectral transmittance of each sample, obtain the typical case of each sample of 1mm thickness
The transmitance of wavelength.
Table 3-4 shows described glass when 1mm thickness, the transmittance values of glass of the present invention, it can be verified that described glass
Glass all has the excellent properties correcting glass as the colour sensitivity for quasiconductor image-forming component.
Table 3
Table 4
Fig. 1 is the spectral-transmission favtor curve chart of above-described embodiment 1.It can be seen that be the feelings of 1mm at thickness of glass
Under condition, the absorbance of optimal wavelength 400nm is more than 80%.In spectral transmittance in the wave-length coverage of 500 to 700nm,
The wave-length coverage corresponding when being 50% of transmitance is 615 ± 10nm.In the spectral-transmission favtor of wavelength 400-1200nm, wavelength
The absorbance of the wavelength zone of 800-1000nm is minimum.Because this region is near-infrared region, semiconductor camera element is in this region
Sensitivity be not the lowest, it is therefore necessary to suppression colour correction light filter absorbance so that it is reach substantially low degree.And work as
Wavelength is when the region of 1000-1200nm, and the sensitivity relative reduction of quasiconductor image-forming component, therefore the glass of the present invention is saturating
The rate of penetrating increased.
Claims (16)
1. near-infrared absorption glass, it is characterised in that: its component represents the P containing 15-35% by cation5+；5-20%'s
Al3+；The Li of 1-30%+；The Na of 0-10%+；The K of 0-3%+；The Cu of 0.1-8%2+；The Mg of 0.1-10%2+；The Ca of 1-20%2+；
The Sr of 15-35%2+；The Ba of 10-30%2+；The O simultaneously represented containing useful anion2-And F-。
2. near-infrared absorption glass as claimed in claim 1, it is characterised in that: containing the P of 20-30%5+；And/or 10-
The Al of 15%3+；And/or the Li of 1-20%+；And/or the Na of 0-5%+；And/or the Cu of 1.2-5%2+；And/or the Mg of 2-8%2+；
And/or the Ca of 5-15%2+；And/or the Sr of 21-30%2+；And/or the Ba of 15-30%2+。
3. near-infrared absorption glass as claimed in claim 1, it is characterised in that: containing the P of 21-25%5+；And/or 2-
The Li of 10%+；And/or the Na of 0.5-3%+；And/or the Cu of 1.8-3%2+；And/or the Mg of 3-7%2+；And/or 7-11%
Ca2+；And/or the Sr of 23-28%2+；And/or the Ba of 21-25%2+。
4. near-infrared absorption glass as claimed in claim 1, it is characterised in that: R2+Content is 30-65%, described R2+Represent
Mg2+、Ca2+、Sr2+And Ba2+Sum.
5. near-infrared absorption glass as claimed in claim 1, it is characterised in that: R2+Content is 40-65%, described R2+Represent
Mg2+、Ca2+、Sr2+And Ba2+Sum.
6. near-infrared absorption glass as claimed in claim 1, it is characterised in that: R2+Content is 54-65%, described R2+Represent
Mg2+、Ca2+、Sr2+And Ba2+Sum.
7. near-infrared absorption glass as claimed in claim 1, it is characterised in that: R2+Content is 54-60%, described R2+Represent
Mg2+、Ca2+、Sr2+And Ba2+Sum.
8. near-infrared absorption glass as claimed in claim 1, it is characterised in that: F-Content is 45-60%；O2-Content is
40-55%.
9. near-infrared absorption glass as claimed in claim 1, it is characterised in that: F-Content is 48-57%；O2-Content is
43-52%.
10. near-infrared absorption glass as claimed in claim 1, it is characterised in that: F-Content is big 50% but is less than or equal to
57%；O2-Content is more than or equal to 43% but less than 50%.
11. near-infrared absorption glass as claimed in claim 1, it is characterised in that: F-Content is 51-55%；O2-Content is
45-49%.
12. near-infrared absorption glass as claimed in claim 1, it is characterised in that: F-Content is 51-53%；O2-Content is
47-49%.
13. as described in claim 1-12 is arbitrary near-infrared absorption glass, it is characterised in that: when the thickness of glass is 1mm,
Wavelength 400nm absorbance shows more than 80%, shows more than 85% in wavelength 500nm absorbance, described near-infrared absorption glass
The crystallize ceiling temperature of glass is below 650 DEG C.
The 14. near-infrared absorption glass as described in claim 1-12 is arbitrary, it is characterised in that described near-infrared absorption glass
During glass thickness 1mm, show more than 88% in wavelength 400nm absorbance, show more than 90% in wavelength 500nm absorbance, described
The crystallize ceiling temperature of near-infrared absorption glass is below 600 DEG C.
15. near-infrared absorption elements, it is characterised in that by the near infrared light described in any claim in claim 1-14
Heat absorbing glass is constituted.
16. near-infrared absorption light filters, it is characterised in that by the near-infrared described in any claim in claim 1-14
Light heat absorbing glass is constituted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610239348.5A CN105906204A (en) | 2012-02-17 | 2012-02-17 | Near-infrared absorption glass, element and light filter |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610239348.5A CN105906204A (en) | 2012-02-17 | 2012-02-17 | Near-infrared absorption glass, element and light filter |
| CN2012100368565A CN102603187A (en) | 2012-02-17 | 2012-02-17 | Near infrared light absorption glass, element and light filter |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2012100368565A Division CN102603187A (en) | 2012-02-17 | 2012-02-17 | Near infrared light absorption glass, element and light filter |
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| CN105906204A true CN105906204A (en) | 2016-08-31 |
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| CN201610239348.5A Pending CN105906204A (en) | 2012-02-17 | 2012-02-17 | Near-infrared absorption glass, element and light filter |
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| CN2012100368565A Pending CN102603187A (en) | 2012-02-17 | 2012-02-17 | Near infrared light absorption glass, element and light filter |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194589A (en) * | 2019-06-25 | 2019-09-03 | 成都光明光电股份有限公司 | Near-infrared absorption glass, glassware, element and optical filter |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013120420A1 (en) * | 2012-02-17 | 2013-08-22 | 成都光明光电股份有限公司 | Near infrared light absorbing glass, element and filter |
| JP6687027B2 (en) * | 2015-07-24 | 2020-04-22 | Ａｇｃ株式会社 | Near infrared cut filter glass |
| CN109748497B (en) * | 2017-11-02 | 2023-09-08 | Hoya株式会社 | Optical glass and optical element |
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|---|---|---|---|---|
| JPH01219037A (en) * | 1988-02-29 | 1989-09-01 | Hoya Corp | Fluorophosphate glass |
| JPH02204342A (en) * | 1989-01-31 | 1990-08-14 | Hoya Corp | Near infrared absorption filter glass |
| CN101613184A (en) * | 2008-06-27 | 2009-12-30 | Hoya株式会社 | Opticglass |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7192897B2 (en) * | 2002-07-05 | 2007-03-20 | 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 |
| CN1944302A (en) * | 2005-09-06 | 2007-04-11 | Hoya株式会社 | Near-infrared-absorbing glass, near-infrared-absorbing element having the same and image-sensing device |
| JP2007091537A (en) * | 2005-09-29 | 2007-04-12 | Hoya Corp | Near-infrared light absorbing glass material lot and method for manufacturing optical element by using the same |
| JPWO2010119964A1 (en) * | 2009-04-17 | 2012-10-22 | 旭硝子株式会社 | Near-infrared cut filter glass |
| JP2011132077A (en) * | 2009-12-25 | 2011-07-07 | Hoya Corp | Near-infrared light absorbing glass, near-infrared light absorbing filter, and imaging device |
| WO2012018026A1 (en) * | 2010-08-03 | 2012-02-09 | 旭硝子株式会社 | Near-infrared cut filter glass and process for manufacturing same |
-
2012
- 2012-02-17 CN CN2012100368565A patent/CN102603187A/en active Pending
- 2012-02-17 CN CN201610239348.5A patent/CN105906204A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01219037A (en) * | 1988-02-29 | 1989-09-01 | Hoya Corp | Fluorophosphate glass |
| JPH02204342A (en) * | 1989-01-31 | 1990-08-14 | Hoya Corp | Near infrared absorption filter glass |
| CN101613184A (en) * | 2008-06-27 | 2009-12-30 | Hoya株式会社 | Opticglass |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194589A (en) * | 2019-06-25 | 2019-09-03 | 成都光明光电股份有限公司 | Near-infrared absorption glass, glassware, element and optical filter |
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