CN102603187A - Near infrared light absorption glass, element and light filter - Google Patents
Near infrared light absorption glass, element and light filter Download PDFInfo
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- CN102603187A CN102603187A CN2012100368565A CN201210036856A CN102603187A CN 102603187 A CN102603187 A CN 102603187A CN 2012100368565 A CN2012100368565 A CN 2012100368565A CN 201210036856 A CN201210036856 A CN 201210036856A CN 102603187 A CN102603187 A CN 102603187A
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- near infrared
- infrared light
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- content
- heat absorbing
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- 239000011521 glass Substances 0.000 title claims abstract description 128
- 230000031700 light absorption Effects 0.000 title claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 238000004031 devitrification Methods 0.000 abstract description 17
- 230000005540 biological transmission Effects 0.000 abstract description 10
- -1 P<5+> Chemical class 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 28
- 230000003595 spectral effect Effects 0.000 description 23
- 238000002834 transmittance Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000012937 correction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000146 host glass Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 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
- 238000012360 testing method Methods 0.000 description 2
- 230000000007 visual effect Effects 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010018612 Gonorrhoea Diseases 0.000 description 1
- 238000003723 Smelting Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 231100000740 envenomation Toxicity 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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
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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
The invention provides near infrared light absorption glass, an element and a light filter with excellent devitrification resistance and excellent transmission characteristics in a visible range. For the near infrared light absorption glass, when the thickness of the near infrared light absorption glass is 1 mm, the transmissivity is shown to be greater than 80% at a wavelength of 400 nm, and the transmissivity is shown to be greater than 85% at a wavelength of 500 nm. The ceiling temperature of crystallization for the near infrared light absorption glass is below 650 DEG C. The near infrared light absorption glass contains cations such as P<5+>, Al<3+>, Li<+>, R<2+> and Cu<2+>, wherein R<2+> represents Mg<2+>, Ca<2+>, Sr<2+> and Ba<2+>, and the content of the R<2+> is 30-60 percent, and in addition, the near infrared light absorption glass contains anions such as O<2-> and F<->.
Description
Technical field
The present invention relates to a kind of near infrared light heat absorbing glass, near infrared light absorber element and near infrared light absorption filter.Particularly, the near infrared light absorption filter that the present invention relates to a kind of suitable chromatic sensitivity correction is with, near infrared light heat absorbing glass that anti-devitrification behavior is good, and the near infrared light absorber element and the spectral filter that are made up of this glass.
Background technology
In recent years; The spectrum sensitivity that is used for the semiconductor camera element such as CCD, CMOS of digital camera and VTR photographic camera; Spread near the near infrared field that begins from visual field the 1100nm, use the spectral filter that absorbs near infrared field light can obtain being similar to people's visual sense degree.Therefore, the chromatic sensitivity correction is increasing with the demand of spectral filter, and this just has higher requirement to the near infrared light absorptive function glass that is used to make this type of spectral filter, promptly require this type of glass have visible range excellent see through characteristic.
In the prior art, near-infrared absorbing glass is through in phosphate glass or fluorphosphate glass, adding Cu
2+Make the near infrared light heat absorbing glass.But relative fluorphosphate glass, the phosphate glass chemicalstability is relatively poor, if glass is exposed under the hot and humid environment for a long time, glass surface can produce the defective of be full of cracks and gonorrhoea.
Summary of the invention
Technical problem to be solved by this invention provides a kind ofly has superior anti-increased devitrification resistance and at excellent near infrared light heat absorbing glass, element and the spectral filter that sees through characteristic of visible range.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the near infrared light heat absorbing glass; When the thickness of said near infrared light heat absorbing glass is 1mm; Show greater than 80% in wavelength 400nm transsmissivity; Show that in wavelength 500nm transsmissivity the crystallization ceiling temperature of said near infrared light heat absorbing glass is below 650 ℃ greater than 85%, said near infrared light heat absorbing glass contains the P that useful cation form shows
5+, Al
3+, Li
+, R
2+And Cu
2+, said R
2+Represent Mg
2+, Ca
2+, Sr
2+And Ba
2+, and R
2+Content is 30-65%, contains the O that useful anion form shows simultaneously
2-And F
-
Further, when said near infrared light heat absorbing glass thickness is 1mm, show greater than 88%, show that in wavelength 500nm transsmissivity the crystallization ceiling temperature of said near infrared light heat absorbing glass is below 600 ℃ greater than 90% in wavelength 400nm transsmissivity.
Further, the P that contains 15-35%
5+The Al of 5-20%
3+The Li of 1-30%
+The Na of 0-10%
+The K of 0-3%
+The Cu of 0.1-8%
2+R
2+Content is 30-65%.
Further, the P that contains 20-30%
5+The Al of 10-15%
3+The Li of 1-20%
+The Na of 0-5%
+The K of 0-3%
+The Cu of 1.2-5%
2+R
2+Content is 40-65%.
Further, the P that contains 21-25%
5+The Al of 10-15%
3+The Li of 2-10%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+R
2+Content is 54-65%.
Further, the P that contains 21-25%
5+The Al of 10-15%
3+The Li of 2-5%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+R
2+Content is 54-60%.
Further, the P that contains 15-35%
5+The Al of 5-20%
3+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+
Further, the P that contains 20-30%
5+The Al of 10-15%
3+The Li of 1-20%
+The Na of 0-5%
+The K of 0-3%
+The Cu of 1.2-5%
2+The Mg of 2-8%
2+The Ca of 5-15%
2+The Sr of 21-30%
2+The Ba of 15-30%
2+
Further, the P that contains 21-25%
5+The Al of 10-15%
3+The Li of 2-10%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+The Mg of 3-7%
2+The Ca of 7-11%
2+The Sr of 23-28%
2+The Ba of 21-30%
2+
Further, the P that contains 21-25%
5+The Al of 10-15%
3+The Li of 2-5%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+The Mg of 3-7%
2+The Ca of 7-11%
2+The Sr of 23-28%
2+The Ba of 21-25%
2+
Further, it is characterized in that F
-Content is 45-60%; O
2-Content is 40-55%.
Further, F
-Content is 48-57%; O
2-Content is 43-52%.
Further, F
-Content is greater than 50% but is less than or equal to 57%; O
2-Content is more than or equal to 43% but less than 50%.
Further, F
-Content is 51-55%; O
2-Content is 45-49%.
Further, F
-Content is 51-53%; O
2-Content is 47-49%.
The near infrared light absorber element is made up of above-mentioned near infrared light heat absorbing glass.
The near infrared light absorption filter is made up of above-mentioned near infrared light heat absorbing glass.
The invention has the beneficial effects as follows: the present invention with fluophosphate glass as host glass, the R in forming through control fluorophosphate host glass
2+Content when improving the anti-increased devitrification resistance of glass, can strengthen the alkali content of glass metal, suppresses Cu
2+Be reduced into Cu
+, make that the near infrared light absorptive character of glass are excellent.When thickness of glass of the present invention is 1mm, show greater than 80%, show greater than 85% that in the spectral transmittance in 500 to 700nm wavelength region, transmitance is that 50% o'clock corresponding wavelength (is λ in wavelength 500nm transsmissivity in wavelength 400nm transsmissivity
50Corresponding wavelength value) scope is the scope of 615 ± 10nm.
Description of drawings
Fig. 1 is the spectral-transmission favtor graphic representation of the near infrared light heat absorbing glass of embodiments of the invention 1.
Embodiment
Near infrared light heat absorbing glass of the present invention be fluophosphate glass as the basis, be added with the Cu of near infrared light sorption
2+Obtain.
Hereinafter, cationic components content representes that with the degree that this positively charged ion weight accounts for whole positively charged ion gross weights anionic group content is represented with the degree that this negatively charged ion weight accounts for whole negatively charged ion gross weights.
P
5+Being the basal component of fluorphosphate glass, is in region of ultra-red, to produce a kind of important component that absorbs.When its content less than 15% the time, glass near infrared light assimilation effect reduces, the colour correction function worsens that also band is green; Surpass 35% anti-increased devitrification resistance of glass and chemicalstability and all worsen, so P
5+Content be defined as 15-35%, be preferably 20-30%, more preferably 21-25%.
Al
3+It is a kind of component of the one-tenth glass property that improves fluorphosphate glass, chemicalstability, resistance to sudden heating.Work as Al
3+Content is lower than at 5% o'clock, does not reach above-mentioned effect; Work as Al
3+Content surpasses at 20% o'clock, and the near-infrared absorbing characteristic reduces.Therefore, Al
3+Content is 5-20%, more preferably 10-15%.
Li
+, Na
+And K
+Be the meltability that improves glass, the component that becomes the transmitance of glass property and visible region.With respect to Na
+, K
+, a spot of Li
+Introducing to the chemicalstability better effects if of glass.But work as Li
+Content surpasses at 30% o'clock, and the chemicalstability of glass and processing characteristics worsen.Therefore, Li
+Content is 1-30%, is preferably 1-20%, more preferably 2-10%, most preferably 2-5%.
The present invention preferably adds minor N a
+With Li
+Consolute can effectively improve the chemicalstability of glass.Na
+The introducing effect that improves meltbility and anti-increased devitrification resistance in addition, its content is 0-10%, is preferably 0-5%, more preferably 0.5-3%.K
+Content is 0-3%, if its content surpasses at 3% o'clock, glass chemistry stability and processing characteristics reduce on the contrary.
R
2+Be the component that effectively improves the one-tenth glass property of glass, anti-increased devitrification resistance and workability, R here
2+Represent Mg
2+, Ca
2+, Sr
2+And Ba
2+As the near infrared light absorption filter, the light transmission rate that is contemplated to be visible range is higher.In order to improve the transmitance of visible range, the cupric ion of introducing in the glass is not Cu
+, must be Cu
2+If glass solution is in reduced state, Cu
2+Just become Cu
+, consequently near the transmitance the wavelength 400nm will reduce.The present invention is through an amount of Mg that strengthens
2+, Ca
2+, Sr
2+And Ba
2+The total amount, increased the alkali content of glass metal, can suppress Cu
2+Be reduced into Cu
+, make that the near infrared light absorptive character of glass are excellent.Mg
2+, Ca
2+, Sr
2+And Ba
2+If the total amount less than 30%, anti-increased devitrification resistance just has the tendency of deterioration, if surpass 65%, the tendency that worsens anti-increased devitrification resistance is arranged also.Therefore, Mg
2+, Ca
2+, Sr
2+And Ba
2+Adding up to amount is 3065%, and preferably adding up to amount is 40-65%, and more preferably to add up to amount be greater than 50% but be less than or equal to 65%, and further preferred to add up to amount be 54-65%, and most preferably adding up to content is 54-60%.
Wherein, Mg
2+And Ca
2+The effect that improves the anti-increased devitrification resistance of glass, chemicalstability, processibility is arranged.Mg
2+Amount is that 0.1-10% is more satisfactory, more preferably 2-8%, further preferred 3-7%.Ca
2+Content is preferably 1-20%, and more preferably 5-15% further is preferably 7-11%.
Relative Mg
2+And Ca
2+, the present invention has introduced high-load Sr
2+And Ba
2+, effectively increasing R
2+Content brings when improving the light transmission rate effect Sr
2+And Ba
2+Also have and improve the effect that glass becomes glass property, anti-increased devitrification resistance, meltbility.Sr
2+Content is preferably 15-35%, 21-30% more preferably, further preferred 23-28%.Same reason, Ba
2+Content is preferably 10-30%, and more preferably 15-30% further is preferably 21-30%, most preferably is 21-25%.
Copper in the glass of the present invention is the leading indicator of near-infrared absorbing characteristic, and with Cu
2+Exist.Work as Cu
2+Content is lower than at 0.1% o'clock, as the near infrared light absorption filter, can not fully reach necessary near infrared light assimilation effect; But when its content surpassed 8%, the anti-increased devitrification resistance of glass, one-tenth glass property all reduced.Therefore, Cu
2+Content is 0.1-8%, is preferably 1.2-5%, more preferably 1.8-3%.
Contain O in the glass of the present invention as anionic component
2-And F
-In near-infrared absorbing glass, when improving melt temperature, Cu
2+Be reduced to Cu easily
+, the color of glass becomes green from blueness, thereby has damaged colour sensitivity correct application necessary characteristic to the semi-conductor image-forming component.
F
-It is the important anionic group that reduces the glass melting temperature and improve chemicalstability.Among the present invention, work as F
-Content was equal to or less than 45% o'clock, and chemicalstability reduces; Work as F
-Content surpasses at 60% o'clock, because O
2-Content reduces, Cu
2+Minimizing can not get suppressing, near 400nm, can produce Cu
2+What cause is painted.Therefore, F
-Content is 45-60%, is preferably 48-57%, more preferably greater than 50% but be less than or equal to 57%, further is preferably 51-55%, more preferably 51-53%.
O
2-Be a kind of important anionic group in the glass of the present invention, its content is that the negatively charged ion total content deducts F
-The remaining whole content in back.Work as O
2-Content very little the time, because Cu
2+Be reduced to C
U+So in the short wavelength zone, particularly near the absorption 400nm becomes more greatly up to shown in green; But work as O
2-Content when too much, thereby cause higher melt temperature because the viscosity of glass becomes higher, so transmitance reduces.Therefore, O among the present invention
2-Content be 40-55%, preferable range is 43-52%, more preferably greater than or equal 43% but, further be preferably 45-49% less than 50%, most preferably be 47-49%.
The present invention is preferably through an amount of F that increases
-Content, and F
-Content is greater than O
2-Content can reduce the glass melting temperature effectively, and increases F in right amount
-Can also make the chemicalstability of glass excellent, F
--O
2-Preferable range be 0.1-20%, further preferable range is 0.1-10%, most preferred range is 0.1-3%.
The present invention is through specific design of components, and light transmission rate is following:
When thickness of glass is 1mm, characteristics showed below the spectral transmittance in 400 to 1200nm wavelength region has.
The spectral transmittance of the wavelength of 400nm more than or equal to 80%, be preferably greater than or equal 85%, more preferably greater than or equal 88%.
The spectral transmittance of the wavelength of 500nm more than or equal to 85%, be preferably greater than or equal 88%, more preferably greater than or equal 90%.
The spectral transmittance of the wavelength of 600nm more than or equal to 58%, be preferably greater than or equal 61%, more preferably greater than or equal 64%.
Be less than or equal to 12% at the spectral transmittance of the wavelength of 700nm, preferably be less than or equal to 10%, be more preferably less than or equal 9%.
Be less than or equal to 5% at the spectral transmittance of the wavelength of 800nm, preferably be less than or equal to 3%, be more preferably less than or equal 2.5%, also be more preferably less than or equal 2%.
Be less than or equal to 5% at the spectral transmittance of the wavelength of 900nm, preferably be less than or equal to 3%, be more preferably less than or equal 2.5%.
Be less than or equal to 7% at the spectral transmittance of the wavelength of 1000nm, preferably be less than or equal to 6%, be more preferably less than or equal 5%.
Be less than or equal to 15% at the spectral transmittance of the wavelength of 1100nm, preferably be less than or equal to 13%, be more preferably less than or equal 11%.
Be less than or equal to 24% at the spectral transmittance of the wavelength of 1200nm, preferably be less than or equal to 22%, be more preferably less than or equal 21%.
That is, the absorption in the near infrared region wavelength region of 700nm to 1200nm is big, and the absorption in the wavelength region of the visible region of 400nm to 600nm is little.
In the spectral transmittance in 500 to 700nm wavelength region, transmitance is that 50% o'clock corresponding wavelength (is λ
50Corresponding wavelength value) scope is 615 ± 10nm.
The transmitance of glass of the present invention is meant the value that obtains in this way through spectrophotometer: the supposition glass sample has two planes of parallel and optical polish; Light vertical incidence from the parallel planes; From the outgoing of another one parallel planes; This outgoing light intensity is exactly a transmitance divided by the incident light intensity, and this transmitance is also referred to as outer transmitance.
According to the above-mentioned characteristic of glass of the present invention, can realize the color correction of semi-conductor image-forming component such as CCD or CMOS admirably.
Near infrared light heat absorbing glass of the present invention possesses the controlled transmission characteristics of above-mentioned that kind in order in optical filter etc., to use.But,, can produce baneful influence to transmission characteristics if in the glass smelting process, produce crystal.Therefore, the anti-increased devitrification resistance key property that should possess for the near infrared light heat absorbing glass.Anti-increased devitrification resistance can be estimated according to the crystallization ceiling temperature, and the crystallization ceiling temperature that reduces glass just can improve the anti-increased devitrification resistance of glass.If the crystallization ceiling temperature uprises, then when being shaped to glass forming body, must improve mold temperature to avoid devitrification by melten glass; At this moment, the moulding of the glass difficulty that becomes, perhaps the glass adhesion during moulding reduces; In becoming the melten glass of glass forming body, convection current takes place, produce brush line, perhaps the volatilization in the glass becomes obvious; The envenomation of glass forming body, perhaps volatile matter adheres on formed body, produces pollution problems.
Glass of the present invention has good transmission characteristics; The crystallization ceiling temperature can be controlled at below 680 ℃ simultaneously, preferably is controlled at below 650 ℃, more preferably is controlled at below 640 ℃; The range of choice of condition of molding enlarges like this, obtains good near infrared light heat absorbing glass simultaneously easily.
The crystallization property of above-mentioned glass adopts temperature gradient furnace method to measure; Specifically: the sample of glass being processed 180*10*10mm; The side polishing; Put into the stove insulation that has thermograde and take out after 4 hours, examine under a microscope the devitrification of glass situation, the crystallization ceiling temperature that the corresponding top temperature of crystal is glass appears in glass.
In addition because the glass transformation temperature of near infrared light heat absorbing glass of the present invention is below 358 ℃, therefore, through can molded lens behind the precision press molding, the optical element of diffraction grating etc.
The characteristic of the chemicalstability aspect of glass is following: the stable D of water-fast effect
WCan reach 1 grade; The stable D of acidproof effect
AReach 4 grades, preferably reach 3 grades, more preferably reach 2 grades.
The stable D of above-mentioned water-fast effect
W(powder method) pressed the testing method of GB/T17129, according to computes:
D
W＝(B-C)/(B-A)*100
In the formula: D
W-glass leaches percentage ratio (%)
The quality of B-strainer and sample (g)
C-strainer and the quality (g) that corrodes the back sample
A-filter quality (g)
By the leaching percentage ratio that calculates, D is stablized in the water-fast effect of opticglass
WBeing divided into 6 types sees the following form.
| Classification | 1 | 2 | 3 | 4 | 5 | 6 |
| Leach percentage ratio (D W) | ＜0.04 | 0.04-0.10 | 0.10-0.25 | 0.25-0.60 | 0.60-1.10 | ＞1.10 |
The stable D of above-mentioned acidproof effect
A(powder method) pressed the testing method of GB/T17129, according to computes:
D
A＝(B-C)/(B-A)*100
In the formula: D
A-glass leaches percentage ratio (%)
The quality of B-strainer and sample (g)
C-strainer and the quality (g) that corrodes the back sample
A-filter quality (g)
By the leaching percentage ratio that calculates, D is stablized in the acidproof effect of opticglass
ABeing divided into 6 types sees the following form.
| Classification | 1 | 2 | 3 | 4 | 5 | 6 |
| Leach percentage ratio (D A) | ＜0.20 | 0.20-0.35 | 0.35-0.65 | 0.65-1.20 | 1.20-2.20 | ＞2.20 |
Involved in the present invention to the near infrared light absorber element constitute by said near infrared light heat absorbing glass; Can give an example out the laminal glass elements that is used for the near infrared light absorption filter or lens etc.; Be applicable to the colour correction purposes of solid-state imager, possess good transmission performance and chemicalstability.
Involved in the present invention to the near infrared spectral filter be the near infrared light absorber element that constitutes by the near infrared light heat absorbing glass, therefore also possess good light transmission performance and chemicalstability.
Embodiment
Hereinafter, reference implementation example will be described the present invention in more detail.Yet, the invention is not restricted to said embodiment.
At first, as frit, raw material weighed is the glass that has in table 1 and table 2 composition that shows with fluorochemical, metaphosphate, oxide compound, nitrate salt and carbonate; After mixing fully; Mixing raw material is put in the platinum crucible with sealing of lid, and heating and melting under 700-900 ℃ temperature is after oxygen protection while homogenizing is adopted in clarification; Melten glass is flowed out with constant flow rate from the temperature control pipeline continuously, obtain opticglass of the present invention after the moulding.
Embodiment 1-15 (the manufacturing embodiment of near-infrared absorbing glass)
Table 1
Table 2
R among the table 1-2
2+For: Mg
2+, Ca
2+, Sr
2+And K
2+Total content.
Above-mentioned glass processing is become tabular; And optical polish is used to measure transmitance with preparation sample is carried out on two sides respect to one another; Use the spectral transmission appearance to measure the spectral transmittance of each sample, obtain the transmitance of typical wavelengths of each sample of 1mm thickness.
Shown said glass when 1mm thickness among the table 3-4, the transmittance values of glass of the present invention can confirm that said glass all has the excellent properties of proofreading and correct glass as the colour sensitivity that is used for the semi-conductor image-forming component.
Table 3
Table 4
Fig. 1 is the spectral-transmission favtor graphic representation of the foregoing description 1.As can be seen from the figure, be under the situation of 1mm at thickness of glass, the transsmissivity of optimal wavelength 400nm is more than 80%.In the spectral transmittance in 500 to 700nm wavelength region, transmitance is that 50% o'clock corresponding wavelength region is 615 ± 10nm.In the spectral-transmission favtor of wavelength 400-1200nm, the transsmissivity of the wavelength zone of wavelength 800-1000nm is minimum.Because this zone is a near-infrared region, semiconductor camera element is not very low at this regional susceptibility, therefore must suppress the transsmissivity of colour correction with spectral filter, makes it reach fully low degree.And when wavelength during at 1000-1200nm regional, the susceptibility of semi-conductor image-forming component reduces relatively, and therefore the transsmissivity of glass of the present invention increases to some extent.
Claims (17)
1. near infrared light heat absorbing glass; It is characterized in that; When the thickness of said near infrared light heat absorbing glass is 1mm, show greater than 80%, show greater than 85% in wavelength 500nm transsmissivity in wavelength 400nm transsmissivity; The crystallization ceiling temperature of said near infrared light heat absorbing glass is below 650 ℃, and said near infrared light heat absorbing glass contains the P that useful cation form shows
5+, Al
3+, Li
+, R
2+And Cu
2+, said R
2+Represent Mg
2+, Ca
2+, Sr
2+And Ba
2+, and R
2+Content is 30-65%, contains the O that useful anion form shows simultaneously
2-And F
-
2. near infrared light heat absorbing glass as claimed in claim 1; It is characterized in that; When said near infrared light heat absorbing glass thickness is 1mm; Show greater than 88% in wavelength 400nm transsmissivity, show that in wavelength 500nm transsmissivity the crystallization ceiling temperature of said near infrared light heat absorbing glass is below 600 ℃ greater than 90%.
3. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 15-35%
5+The Al of 5-20%
3+The Li of 1-30%
+The Na of 0-10%
+The K of 0-3%
+The Cu of 0.1-8%
2+R
2+Content is 30-65%.
4. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 20-30%
5+The Al of 10-15%
3+The Li of 1-20%
+The Na of 0-5%
+The K of 0-3%
+The Cu of 1.2-5%
2+R
2+Content is 40-65%.
5. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 21-25%
5+The Al of 10-15%
3+The Li of 2-10%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+R
2+Content is 54-65%.
6. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 21-25%
5+The Al of 10-15%
3+The Li of 2-5%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+R
2+Content is 54-60%.
7. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 15-35%
5+The Al of 5-20%
3+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+
8. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 20-30%
5+The Al of 10-15%
3+The Li of 1-20%
+The Na of 0-5%
+The K of 0-3%
+The Cu of 1.2-5%
2+The Mg of 2-8%
2+The Ca of 5-15%
2+The Sr of 21-30%
2+The Ba of 15-30%
2+
9. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 21-25%
5+The Al of 10-15%
3+The Li of 2-10%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+The Mg of 3-7%
2+The Ca of 7-11%
2+The Sr of 23-28%
2+The Ba of 21-30%
2+
10. according to claim 1 or claim 2 near infrared light heat absorbing glass is characterized in that, contains the P of 21-25%
5+The Al of 10-15%
3+The Li of 2-5%
+The Na of 0.5-3%
+The Cu of 1.8-3%
2+The Mg of 3-7%
2+The Ca of 7-11%
2+The Sr of 23-28%
2+The Ba of 21-25%
2+
11., it is characterized in that F like the described near infrared light heat absorbing glass of arbitrary claim among the claim 1-10
-Content is 45-60%; O
2-Content is 40-55%.
12., it is characterized in that F like the described near infrared light heat absorbing glass of arbitrary claim among the claim 1-10
-Content is 48-57%; O
2-Content is 43-52%.
13., it is characterized in that F like the described near infrared light heat absorbing glass of arbitrary claim among the claim 1-10
-Content is greater than 50% but is less than or equal to 57%; O
2-Content is more than or equal to 43% but less than 50%.
14., it is characterized in that F like the described near infrared light heat absorbing glass of arbitrary claim among the claim 1-10
-Content is 51-55%; O
2-Content is 45-49%.
15., it is characterized in that F like the described near infrared light heat absorbing glass of arbitrary claim among the claim 1-10
-Content is 51-53%; O
2-Content is 47-49%.
16. the near infrared light absorber element is characterized in that, is made up of the described near infrared light heat absorbing glass of arbitrary claim among the claim 1-15.
17. the near infrared light absorption filter is characterized in that, is made up of the described near infrared light heat absorbing glass of arbitrary claim among the claim 1-15.
Priority Applications (6)
| 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 |
| PCT/CN2013/071331 WO2013120420A1 (en) | 2012-02-17 | 2013-02-04 | Near infrared light absorbing glass, element and filter |
| KR1020147025861A KR20140133864A (en) | 2012-02-17 | 2013-02-04 | Near infrared light absorbing glass, element and filter |
| KR1020167016302A KR20160075854A (en) | 2012-02-17 | 2013-02-04 | Near infrared light absorbing glass, element and filter |
| JP2014556908A JP6001094B2 (en) | 2012-02-17 | 2013-02-04 | Near infrared light absorbing glass, near infrared light absorbing element, and near infrared light absorbing optical filter |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100368565A CN102603187A (en) | 2012-02-17 | 2012-02-17 | Near infrared light absorption glass, element and light filter |
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| CN201610239348.5A Division CN105906204A (en) | 2012-02-17 | 2012-02-17 | Near-infrared absorption glass, element and light filter |
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| CN102603187A true CN102603187A (en) | 2012-07-25 |
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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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| CN201610239348.5A Pending CN105906204A (en) | 2012-02-17 | 2012-02-17 | Near-infrared absorption glass, element and light filter |
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Cited By (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 |
| CN107850711A (en) * | 2015-07-24 | 2018-03-27 | 旭硝子株式会社 | Near infrared cut-off filters glass |
| CN109748497A (en) * | 2017-11-02 | 2019-05-14 | Hoya株式会社 | Optical glass and optical element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194589B (en) * | 2019-06-25 | 2022-02-01 | 成都光明光电股份有限公司 | Near-infrared light absorbing glass, glass product, element and optical filter |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101613184B (en) * | 2008-06-27 | 2013-07-24 | Hoya株式会社 | Optical glass |
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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 |
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| 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 |
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| 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 |
Cited By (4)
| 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 |
| CN107850711A (en) * | 2015-07-24 | 2018-03-27 | 旭硝子株式会社 | Near infrared cut-off filters glass |
| CN109748497A (en) * | 2017-11-02 | 2019-05-14 | Hoya株式会社 | Optical glass and optical element |
| CN109748497B (en) * | 2017-11-02 | 2023-09-08 | Hoya株式会社 | Optical glass and optical element |
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| CN105906204A (en) | 2016-08-31 |
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