WO2011071157A1 - Verre filtrant bloquant les rayons infrarouges proches - Google Patents

Verre filtrant bloquant les rayons infrarouges proches Download PDF

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Publication number
WO2011071157A1
WO2011071157A1 PCT/JP2010/072271 JP2010072271W WO2011071157A1 WO 2011071157 A1 WO2011071157 A1 WO 2011071157A1 JP 2010072271 W JP2010072271 W JP 2010072271W WO 2011071157 A1 WO2011071157 A1 WO 2011071157A1
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WIPO (PCT)
Prior art keywords
glass
temperature
transmittance
infrared cut
cut filter
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PCT/JP2010/072271
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English (en)
Japanese (ja)
Inventor
博之 大川
裕己 近藤
盛輝 大原
雄一 飯田
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旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to CN2010800563158A priority Critical patent/CN102656125A/zh
Priority to JP2011545268A priority patent/JP5048159B2/ja
Publication of WO2011071157A1 publication Critical patent/WO2011071157A1/fr
Priority to US13/489,740 priority patent/US20120241697A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • 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

Definitions

  • the present invention relates to a near-infrared cut filter glass that is used in color correction filters for digital still cameras, color video cameras, and the like, can be reheated at a high temperature, and has excellent solubility and weather resistance.
  • Solid-state imaging devices such as CCDs and CMOSs used for digital still cameras have spectral sensitivity ranging from the visible region to the near infrared region around 1200 nm. Therefore, since excellent color reproducibility cannot be obtained as it is, the visibility is corrected using a near-infrared cut filter glass to which a specific substance that absorbs infrared rays is added.
  • a near-infrared cut filter glass As this near-infrared cut filter glass, an optical glass in which CuO is added to a fluorophosphate glass has been developed and used so that it selectively absorbs wavelengths in the near-infrared region and has high weather resistance.
  • the composition of these glasses is disclosed in Patent Documents 1 to 4.
  • soldering reflow process is often used. More recently, solder that does not contain lead, which is an environmentally hazardous substance, is often used in the reflow process, and these lead-free solders have a higher melting temperature than leaded solder, so the heat treatment temperature in the reflow process tends to increase. It is in.
  • the present invention has been made in view of the above circumstances. Focusing on the crystallization start temperature of glass, heat treatment is performed in a film forming process performed after glass molding, an imaging device manufacturing process using these glasses, and the like. Even if it is a case, it aims at providing the near-infrared cut filter glass which can be used without fear of a crystal
  • the present inventor has studied a glass composition that can increase the crystallization start temperature and lower the liquidus temperature that affects the devitrification property and the transmission property in the visible region of the fluorophosphate glass.
  • a glass composition that can increase the crystallization start temperature in the fluorophosphate-based glass.
  • P 5+ or Al 3+ that is a glass-forming oxide is contained.
  • the liquidus temperature becomes high, and devitrification occurs during melting or fluorine volatilization is promoted, causing striae during molding.
  • Al 3+ is added, the liquidus temperature is further increased, so that the content of Al 3+ is naturally limited and weather resistance cannot be maintained.
  • the present inventor conducted a detailed study on the contents of P 5+ and Al 3+ , and found that when the glass component was P 5+ 25 to 37% and Al 3+ 16.2 to 25% in terms of cation%.
  • the present inventors have found that a near-infrared cut filter glass made of a fluorophosphate-based glass having a high crystallization start temperature and a low liquidus temperature can be obtained.
  • the near-infrared cut filter glass of the present invention is expressed in terms of cation%, P 5+ 25 to 37%, Al 3+ 16.2 to 25%, R + 0.5 to 40% (where R + is Li + , Na +, and represents the total amount of K +), R 2+ 0.5 ⁇ 45% ( provided that, R 2+ is, Mg 2+, Ca 2+, Sr 2+, represents the total amount of Ba 2+, and Zn 2+), It contains Cu 2+ 2 to 10%, Sb 3+ 0 to 1%, and includes O 2 ⁇ 30 to 85% and F ⁇ 15 to 70% in terms of anion%.
  • the near-infrared cut filter glass of the present invention is expressed in terms of cation%, P 5+ 25 to 37%, Al 3+ 16.2 to 25%, Li + 0.5 to 20%, Na + 0.5 to 15%. , K + 0 to 15%, Mg 2+ 0.5 to 12%, Ca 2+ 0.5 to 12%, Sr 2+ 0.5 to 12%, Ba 2+ 0.5 to 12%, Zn 2+ 0 to 12% , Cu 2+ 2 to 10%, Sb 3+ 0 to 1%, and O 2 30 to 85% and F ⁇ 15 to 70% in terms of anion%.
  • the near-infrared cut filter glass of the present invention is characterized in that the crystallization start temperature is 400 to 600 ° C.
  • the near infrared cut filter glass of the present invention is characterized in that the liquidus temperature is 700 to 820 ° C.
  • the near-infrared cut filter glass of the present invention has a transmittance at a wavelength of 400 nm of 75 to 92% when converted so that a wavelength showing a transmittance of 50% is 615 nm in a spectral transmittance at a wavelength of 600 to 700 nm.
  • the transmittance at a wavelength of 700 nm is 5 to 10%
  • the transmittance at a wavelength of 1200 nm is 10 to 20%, and converted to a thickness of 0.3 mm
  • the wavelength indicating a transmittance of 50% is 660 nm. It is characterized by the following.
  • near infrared cut filter glass of the present invention is characterized by containing substantially no PbO, the As 2 O 3, V 2 O 5, LaY 3, YF 3, YbF 3, GdF 3.
  • the crystallization start temperature can be increased.
  • a glass having a high and low liquidus temperature can be obtained, whereby a near-infrared cut filter glass that can be used without fear of occurrence of defects or the like can be provided.
  • each content and total content of the cation component are represented by cation%
  • each content and total content of the anion component are represented by% anion.
  • P 5+ is a main component (glass-forming oxide) that forms glass, and is an essential component for increasing the cutability in the near infrared region and increasing the crystallization start temperature. A sufficient effect cannot be obtained, and if it exceeds 37%, the glass becomes unstable and the weather resistance is lowered, which is not preferable.
  • it is 27 to 35%, more preferably 28 to 34%. More preferably, it is 29 to 33%, and most preferably 30 to 32%.
  • Al 3+ is a main component (glass-forming oxide) that forms glass, and is an essential component for increasing the crystallization start temperature, increasing weather resistance, etc., but its effect is sufficient when it is less than 16.2%. If it exceeds 25%, the glass becomes unstable and the infrared cut property is lowered, which is not preferable. Preferably it is 17 to 20%, more preferably 17.5 to 19%. Note that the use of Al 2 O 3 or Al (PO 3 ) 3 as a raw material for Al 3+ makes the glass unstable by increasing the melting temperature, generating unmelted material, and reducing the amount of F ⁇ charged. Therefore, it is not preferable, and AlF 3 is preferably used.
  • R + (where R + represents the total amount of Li + , Na + and K + ) lowers the melting temperature of the glass, lowers the liquidus temperature of the glass, softens the glass, stabilizes the glass However, if it is less than 0.5%, the effect cannot be sufficiently obtained, and if it exceeds 40%, the glass becomes unstable, which is not preferable.
  • R + represents the total amount of Li + , Na + and K +
  • it is 3 to 37%, more preferably 5 to 34%. More preferably, it is 10 to 31%, and most preferably 15 to 25%.
  • Li + is an essential component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, softening the glass, stabilizing the glass, etc. If it is not sufficiently obtained and exceeds 20%, the glass becomes unstable. Preferably, it is 6 to 18%, more preferably 11 to 15%. Note that it is not preferable to use Li 2 O or LiPO 3 as a Li + raw material because the amount of F ⁇ charged decreases and the glass becomes unstable, and LiF is preferably used.
  • Na + is an essential component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, softening the glass, stabilizing the glass, etc., but the effect is less than 0.5%. If it is not sufficiently obtained and exceeds 15%, the glass becomes unstable, which is not preferable. Preferably it is 3 to 10%, more preferably 5 to 9%.
  • K + is not an essential component, it has effects such as lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, and softening the glass. Absent. Preferably, it is 1 to 9%.
  • R 2+ (where R 2+ represents the total amount of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , and Zn 2+ ) lowers the melting temperature of the glass, lowers the liquidus temperature of the glass, glass It is an essential component for softening the glass, stabilizing the glass, increasing the strength of the glass, etc., but if it is less than 0.5%, the effect cannot be sufficiently obtained, and if it exceeds 45%, the glass becomes unstable. It is not preferable because the infrared cut property is lowered and the strength of the glass is lowered. Preferably it is 6 to 37%, more preferably 9 to 34%. More preferably, it is 12 to 31%, and most preferably 15 to 28%.
  • Mg 2+ is an essential component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, softening the glass, stabilizing the glass, increasing the strength of the glass, etc. If it is less than%, the effect cannot be sufficiently obtained, and if it exceeds 12%, the glass becomes unstable and the infrared cut property is lowered, which is not preferable. Preferably it is 2 to 6%, more preferably 3 to 5%.
  • Ca 2+ is an essential component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, softening the glass, stabilizing the glass, increasing the strength of the glass, etc. If it is less than%, the effect cannot be sufficiently obtained, and if it exceeds 12%, the glass becomes unstable, which is not preferable. Preferably it is 5 to 11%, more preferably 7 to 10%.
  • Sr 2+ is an essential component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, softening the glass, stabilizing the glass, etc., but its effect is less than 0.5%. If it is not sufficiently obtained and exceeds 12%, the strength of the glass is lowered, which is not preferable. Preferably it is 3 to 9%, more preferably 5 to 7%.
  • Ba 2+ is an essential component for lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, softening the glass, stabilizing the glass, etc., but the effect is less than 0.5%. If it is not sufficiently obtained and exceeds 12%, the strength of the glass is lowered, which is not preferable. Preferably it is 3 to 9%, more preferably 4 to 7%.
  • Zn 2+ is not an essential component, it has effects such as lowering the melting temperature of the glass, lowering the liquidus temperature of the glass, and softening the glass. However, if it exceeds 12%, the infrared cut property is lowered. Therefore, it is not preferable.
  • the content is preferably 0 to 5%, and more preferably not contained.
  • Cu 2+ is an essential component for cutting near-infrared rays, but if it is less than 2%, the effect cannot be sufficiently obtained when the thickness of the glass is reduced, and if it exceeds 10%, the visible region transmittance decreases. Therefore, it is not preferable.
  • the content is preferably 2.1 to 8%, more preferably 2.4 to 7%, and still more preferably 2.7 to 6%.
  • corresponds to size reduction and thickness reduction of an imaging device or its mounting apparatus, even if the thickness of glass is thin, a favorable spectral characteristic is acquired.
  • the thickness of the glass is preferably less than 1 mm, more preferably less than 0.8 mm, further preferably less than 0.6 mm, and most preferably less than 0.4 mm. Further, the lower limit value of the glass thickness is not particularly limited, but it is preferably 0.1 mm in consideration of the strength that is difficult to break during the manufacture of the glass or the conveyance during the incorporation into the imaging device.
  • Sb 3+ is not an essential component, it has the effect of increasing the visible region transmittance by reducing the concentration of Cu + ions in the glass having absorption in the vicinity of a wavelength of 300 to 600 nm. This is not preferable because the stability of the is lowered.
  • it is 0 to 1%, more preferably 0.01 to 0.8%. More preferably, it is 0.05 to 0.5, and most preferably 0.1 to 0.3%.
  • O 2 ⁇ is an essential component for stabilizing the glass, increasing the transmittance in the visible region, increasing the mechanical properties such as strength, hardness and elastic modulus, and decreasing the ultraviolet transmittance. If the ratio is less than 85%, the effect cannot be sufficiently obtained, and if it exceeds 85%, the glass becomes unstable, and the weather resistance is lowered. Preferably it is 55 to 75%, more preferably 60 to 70%.
  • F 2 - is an essential component for improving the weather resistance in order to stabilize the glass, but if it is less than 15%, the effect cannot be sufficiently obtained, and if it exceeds 70%, the visible region transmittance is lowered. Further, it is not preferable because mechanical properties such as strength, hardness and elastic modulus may be lowered and ultraviolet transmittance may be increased. Preferably it is 25 to 45%, more preferably 30 to 40%.
  • the glass of the present invention PbO, As 2 O 3, V 2 O 5, LaY 3, YF 3, YbF 3, it is preferred not to substantially contain GdF 3.
  • PbO is a component that lowers the viscosity of the glass and improves manufacturing workability.
  • As 2 O 3 is a component that acts as an excellent clarifier that can generate a clarified gas in a wide temperature range.
  • PbO and As 2 O 3 are environmentally hazardous substances, it is desirable not to contain them as much as possible.
  • V 2 O 5 has absorption in the visible region, it is desirable that V 2 O 5 is not contained as much as possible in the near-infrared cut filter glass for a solid-state imaging device that is required to have a high visible region transmittance.
  • LaY 3 , YF 3 , YbF 3 , and GdF 3 are components that stabilize the glass, but since the raw materials are relatively expensive and lead to increased costs, it is desirable that LaY 3 , YF 3 , YbF 3 , and GdF 3 are not contained as much as possible.
  • substantially not containing means that it is not intended to be used as a raw material, and it is considered that the raw material components and inevitable impurities mixed in from the manufacturing process are not contained.
  • a nitrate compound or a sulfate compound having a cation forming glass can be added as an oxidizing agent or a clarifying agent.
  • the oxidizing agent has an effect of improving the transmittance in the vicinity of a wavelength of 400 to 600 nm.
  • the addition amount of the nitrate compound or sulfate compound is preferably 0.5 to 10% by mass based on the external addition to the raw material mixture. If the addition amount is less than 0.5% by mass, there is no effect of improving the transmittance, and if it exceeds 10% by mass, it becomes difficult to form glass. More preferably, it is 1 to 8% by mass, and still more preferably 3 to 6% by mass.
  • Al (NO 3 ) 3 LiNO 3 , NaNO 3 , KNO 3 , Mg (NO 3 ) 2 , Ca (NO 3 ) 2 , Sr (NO 3 ) 2 , Ba (NO 3 ) 2 , Zn (NO 3 ) 2 , Cu (NO 3 ) 2 and the like.
  • the crystallization start temperature of the near-infrared cut filter glass of the present invention is preferably 400 ° C. or higher. If the crystallization start temperature is less than 400 ° C., crystals are likely to occur. Preferably it is 450 degreeC or more, More preferably, it is 475 degreeC or more. Most preferably, it is 500 degreeC or more. In general, when the crystallization start temperature is too high, the liquidus temperature is also increased. Therefore, the upper limit of the crystallization start temperature is preferably 600 ° C. or less, and more preferably 575 ° C. or less.
  • the near-infrared cut filter glass of the present invention is characterized by finding a fluorophosphate glass composition in which this value is a predetermined value or more by paying attention to the crystallization start temperature of the glass.
  • the crystallization start temperature refers to the first temperature at which glass crystallization occurs after the glass transition point. If the crystallization start temperature is high, it becomes possible to perform heat treatment at a high temperature after glass forming. .
  • a functional film such as an antireflection film (AR coating) or an ultraviolet and infrared cut coating is formed on a near infrared cut filter glass by vapor deposition or sputtering
  • the glass temperature is higher if the crystallization start temperature of the glass is higher.
  • Such a dense film has an advantage that the characteristics do not change even when the glass is heated at a high temperature in a reflow process or the like.
  • the glass ambient temperature is about 250 to 350 ° C. Therefore, the glass temperature during the film forming process for forming the functional film on the glass is the reflow process. It is desirable to carry out at 350 to 450 ° C. or higher, which is higher than the glass temperature at the time, and it is desirable that the crystallization start temperature of the glass is higher than the glass temperature at the time of film formation.
  • the inventor confirmed the change in film properties before and after the reflow process of the near-infrared cut filter glass in which the antireflection film (AR coating) was formed on various glasses, and the presence or absence of crystal precipitation of the glass by the change in transmittance.
  • the glass having a crystallization start temperature of 400 ° C. or higher had a small change in transmittance before and after the reflow process, and a significant difference was observed compared to the glass having a temperature lower than 400 ° C.
  • Near-infrared cut filter glass used for high-end single-lens reflex cameras is desired to have no particular change in spectral characteristics. Taking these into account, the crystallization start temperature of glass is 475 ° C. or higher. It is more preferable that
  • the liquid phase temperature of the near infrared cut filter glass of the present invention is preferably 820 ° C. or lower. If the liquidus temperature of the glass exceeds 820 ° C., the melting temperature and the molding temperature are increased, and striae due to the volatilization of fluorine at the time of melting the glass occurs, so that the yield decreases. Preferably it is 800 degrees C or less, More preferably, it is 780 degrees C or less. Most preferably, it is 760 degrees C or less. In general, when the liquidus temperature is too low, the crystallization start temperature is lowered. Therefore, the lower limit of the liquidus temperature is preferably 700 ° C. or higher, and more preferably 720 ° C. or higher.
  • the near-infrared cut filter glass of the present invention has a transmittance at a wavelength of 400 nm of 75% or more when converted so that a wavelength showing a transmittance of 50% is 615 nm in a spectral transmittance at a wavelength of 600 to 700 nm. It is preferable that the ratio is 82% or more. More preferably, it is 85% or more, and most preferably 87% or more. Considering the loss due to surface reflection at the interface between glass and air, the upper limit of the transmittance at a wavelength of 400 nm is 92%.
  • the near-infrared cut filter for a solid-state imaging device is required to have as high a transmittance in the visible region as possible.
  • the near-infrared cut filter glass of the present invention preferably has a transmittance at a wavelength of 700 nm of 10% or less, more preferably 9% or less, and more preferably 8% or less as an infrared cut property. Is most preferred. Considering Cu 2+ that can be stably added to glass, the lower limit of the transmittance at a wavelength of 700 nm is 5%. Further, the transmittance at a wavelength of 1200 nm is preferably 20% or less, more preferably 18% or less, and most preferably 16% or less.
  • the near-infrared cut filter glass of the present invention preferably has a wavelength of 50% or less at a wavelength of 600 to 700 nm and a wavelength of 660 nm or less when converted to a thickness of 0.3 mm, at a wavelength of 600 to 700 nm. More preferably, it is more preferably 620 nm or less.
  • image processing digital processing
  • the transmittance characteristic in the visible region of the near-infrared cut filter glass of the present invention uses the transmittance characteristic converted so that the wavelength at which the transmittance is 50% is 615 nm. This is because the transmittance of the glass varies depending on the thickness, but if it is a homogeneous glass, the transmittance of a predetermined thickness can be obtained by calculation if the thickness and transmittance of the glass in the direction of light transmission are known. This is because it can.
  • the near-infrared cut filter glass of the present invention is also characterized in that the glass is stable by having the above glass configuration.
  • the stability of the glass includes two things: stability in a temperature range near the liquidus temperature (TL) and stability in a temperature range near the glass transition point (Tg).
  • the stability in the temperature range near the liquidus temperature (TL) is that the liquidus temperature (TL) is low, and the growth of devitrification is slow near the liquidus temperature (TL).
  • the stability in the temperature range near the glass transition point (Tg) is that the crystallization temperature (Tc) and the crystallization start temperature (Tx) are high, and the growth of devitrification is slow in the vicinity of Tc and Tx.
  • the near-infrared cut filter glass of the present invention has a high crystallization start temperature as described above, so that it is difficult to produce crystals even at high temperatures, and since the liquidus temperature is low, the melting temperature of the glass can be lowered and the transmittance in the visible region Therefore, a large amount of visible light can be introduced into the solid-state imaging device. For this reason, it can be suitably used as a near-infrared cut filter glass used for color correction of a solid-state imaging device.
  • the near-infrared cut filter glass of the present invention can be produced as follows. First, the raw materials are weighed and mixed so that the obtained glass has the above composition range. This raw material mixture is placed in a platinum crucible and heated and melted at a temperature of 700 to 1000 ° C. in an electric furnace. After sufficiently stirring and clarifying, it is cast into a mold, slowly cooled, then cut and polished to form a flat plate having a predetermined inner thickness. In the said manufacturing method, it is preferable that the highest temperature of the glass during glass melting shall be 950 degrees C or less.
  • the temperature is more preferably 900 ° C. or lower, and most preferably 850 ° C. or lower.
  • the temperature is too low, crystallization occurs during melting or it takes time to melt, so 700 ° C. or higher is preferable, and 750 ° C. or higher is more preferable.
  • Examples and Comparative Examples of the present invention are shown in Tables 1 to 3.
  • Examples 1 to 12 and Examples 16 to 20 are examples of the present invention, and examples 13 to 15 are comparative examples of the present invention.
  • Example 13 is the glass of Example 2 described in JP-A-2004-83290
  • Example 14 is the glass of Example 11 described in JP-A-2004-83290
  • Example 15 is JP-A 2004-137100. It is the glass of Example 1 of description.
  • the raw materials are weighed and mixed so as to have the compositions shown in Tables 1 to 3 (cation%, anion%), and placed in a platinum crucible having an internal volume of about 300 cc, at 700 to 1000 ° C. for 1 to 3 hours.
  • the sample was cast into a rectangular mold having a length of 50 mm ⁇ width 50 mm ⁇ height 20 mm preheated to about 300 to 500 ° C., and then slowly cooled at about 1 ° C./minute to obtain a sample. About the solubility of glass, etc., it observed visually at the time of the said sample preparation, and it confirmed that the obtained glass sample did not have a bubble and a striae.
  • the raw materials of each glass are H 3 PO 4 or Al (PO 3 ) 3 in the case of P 5+ , AlF 3 , Al (PO 3 ) 3 or A 2 O 3 in the case of Al 3+ , and Li + LiF, LiNO 3 or Li 2 O for Mg 2+ , MgF 2 or MgO for Mg 2+ , SrF 2 or SrCO 3 for Sr 2+ , BaF 2 or BaCO 3 for Ba 2+ , Na + ,
  • fluoride was used, and in the case of Cu 2+ , CuO was used.
  • the blank indicates that the corresponding cation or anion content is 0%.
  • the glass produced as described above was evaluated for the crystallization start temperature, liquidus temperature, transmittance, and weather resistance by the following methods.
  • the crystallization start temperature and the liquidus temperature were measured using a thermal analyzer (trade name: Tg / DTA6300, manufactured by Seiko Instruments Inc.). After preparing about 3g of glass and crushing it with a mortar and pestle, using the sample remaining between the 105 ⁇ m and 44 ⁇ m sieves, measurement was performed at a measurement range of 200-1000 ° C and a temperature measurement of 10 ° C / min. Based on the obtained DTA (Differential Thermal Analysis) curve, the crystallization start temperature was first determined from the portion showing crystallization. The liquidus temperature was determined from the temperature at which the last crystal melts.
  • a thermal analyzer trade name: Tg / DTA6300, manufactured by Seiko Instruments Inc.
  • the transmittance was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by PerkinElmer, trade name: LAMBDA 950). Specifically, a glass sample in which both sides of 20 mm long ⁇ 20 mm wide ⁇ 0.3 mm thick were optically polished was prepared and measured. In addition, the transmittance
  • the weather resistance was measured after holding an optically polished glass sample in a high-temperature and high-humidity tank at 65 ° C. and a relative humidity of 90% for 1000 hours using a high-temperature and high-humidity tank (trade name: SH-221 manufactured by Espec) The burnt state on the glass surface was visually observed, and no burn was observed (no weathering problem).
  • each glass of the examples according to the present invention has a high crystallization start temperature and a low liquidus temperature, and thus heat treatment is performed at a high temperature after glass forming, which is impossible with conventional glass. It is possible.
  • the glass temperature can be increased if the crystallization start temperature is high.
  • a functional film whose characteristics are not changed by a soldering reflow process or the like can be formed.
  • permeability of the visible region of glass is high, and it can use suitably as near infrared cut filter glass for solid-state image sensors.
  • it has the outstanding weather resistance which a fluorophosphate glass has.
  • the glass crystallization start temperature is high, it is possible to perform heat treatment at a high temperature in the processing step after glass forming. For this reason, for example, when a functional film such as an antireflection film (AR coating) or ultraviolet / infrared cut coating is formed on a near-infrared cut filter glass by vapor deposition or sputtering, the glass temperature is increased if the crystallization start temperature is high. Since the film can be made high, a film whose characteristics do not change in a soldering reflow process or the like can be formed, which is useful.
  • AR coating antireflection film
  • ultraviolet / infrared cut coating ultraviolet / infrared cut coating

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Abstract

La présente invention concerne un verre filtrant bloquant les rayons infrarouges proches, qui peut être utilisé sans craindre l'apparition de défauts ou analogues étant donné que les cristaux ne se forment pas facilement dans le verre même dans les cas où un traitement thermique est mis en œuvre au cours d'un processus filmogène qui est exécuté après la formation du verre ou pendant un procédé de fabrication d'un dispositif de capture d'image qui fait intervenir le verre. L'invention concerne plus précisément un verre filtrant bloquant les rayons infrarouges proches, qui est caractérisé en ce qu'il contient, en pourcentage de cations, 25-37 % de P5+, 16,2-25 % d'Al3+, 0,5-40 % de R+ (R+ représente la quantité totale de Li+, Na+ et K+), 0,5-45 % de R2+ (R2+ représente la quantité totale de Mg2+, Ca2+, Sr2+, Ba2+ et Zn2+), 2-10 % de Cu2+, 0-1 % de Sb3+, et en pourcentage d'anions, 30-85 % d'O2- et 15-70 % de F-.
PCT/JP2010/072271 2009-12-11 2010-12-10 Verre filtrant bloquant les rayons infrarouges proches WO2011071157A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2010800563158A CN102656125A (zh) 2009-12-11 2010-12-10 近红外线截止滤光片玻璃
JP2011545268A JP5048159B2 (ja) 2009-12-11 2010-12-10 近赤外線カットフィルタガラス
US13/489,740 US20120241697A1 (en) 2009-12-11 2012-06-06 Near infrared cut filter glass

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Application Number Priority Date Filing Date Title
JP2009-281862 2009-12-11
JP2009281862 2009-12-11
JP2010-152009 2010-07-02
JP2010152009 2010-07-02

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WO2013120420A1 (fr) * 2012-02-17 2013-08-22 成都光明光电股份有限公司 Verre, élément et filtre absorbant la lumière du proche infrarouge
WO2013120421A1 (fr) * 2012-02-17 2013-08-22 成都光明光电股份有限公司 Verre, élément et filtre absorbant la lumière du proche infrarouge
US20130214218A1 (en) * 2012-02-17 2013-08-22 Cdgm Glass Co., Ltd. Near-infrared absorption glass, element and filter
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JP2015522499A (ja) * 2012-04-11 2015-08-06 成都光明光▲電▼股▲分▼有限公司 近赤外光吸収ガラス、近赤外光吸収素子、及び近赤外光吸収光学フィルタ
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CN110937809A (zh) * 2012-05-15 2020-03-31 株式会社小原 光学玻璃、光学元件及预成型体
WO2015156163A1 (fr) * 2014-04-09 2015-10-15 旭硝子株式会社 Verre filtrant destiné à bloquer le rayonnement infrarouge proche
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JP2017014044A (ja) * 2015-06-30 2017-01-19 Hoya株式会社 近赤外線吸収ガラスおよびフィルター
JP2018010275A (ja) * 2016-06-30 2018-01-18 旭硝子株式会社 紫外線透過フィルタ
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JP2020079188A (ja) * 2018-11-14 2020-05-28 株式会社オハラ 光学ガラス、光学素子及びプリフォーム
JP7082936B2 (ja) 2018-11-14 2022-06-09 株式会社オハラ 光学ガラス、光学素子及びプリフォーム
JP2022516920A (ja) * 2019-01-25 2022-03-03 シーディージーエム グラス カンパニー リミテッド フルオロリン酸塩ガラス、ガラスプレフォーム、光学素子及びそれを有する光学機器
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KR20210033914A (ko) 2019-09-19 2021-03-29 제이에스알 가부시끼가이샤 광학 부재 및 카메라 모듈
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JP5048159B2 (ja) 2012-10-17
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