JP2007290886A - Aluminophosphate glass containing copper (ii) oxide, and use thereof for optical filtering - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide aluminophosphate glass having low transmission in the near infrared-ray range with a steep absorption edge. <P>SOLUTION: This Cu-containing aluminophosphate glass comprises, by wt.%, 65-80 P<SB>2</SB>O<SB>5</SB>, 4-20 Al<SB>2</SB>O<SB>3</SB>, 0-5 SiO<SB>2</SB>, 0-<5.5 B<SB>2</SB>O<SB>3</SB>, 0-2.1 Y<SB>2</SB>O<SB>3</SB>, 0-2.1 La<SB>2</SB>O<SB>3</SB>, 0-7.9 MgO, 0-2.5 CaO, 0-2.5 SrO, 0-2.5 BaO, 0-8 ZnO, <18 SR'O, >2-12.5 Li<SB>2</SB>O, 0-6 Na<SB>2</SB>O, 0-4 K<SB>2</SB>O, 0-2.5 Rb<SB>2</SB>O, 0-2.5 Cs<SB>2</SB>O, >2-15 SR"<SB>2</SB>O, 4-24 SR'''<SB>2</SB>O<SB>3</SB>, 5-15 CuO, 0-0.5 V<SB>2</SB>O<SB>5</SB>, and 5-15 SCuO+V<SB>2</SB>O<SB>5</SB>, where SR'O is sum total of ZnO and alkaline earth metal oxides; SR"<SB>2</SB>O is sum total of alkali metal oxides; and SR'''<SB>2</SB>O<SB>3</SB>is sum total of R'''<SB>2</SB>O<SB>3</SB>compounds where R''' is Al, B, Y or La. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a glass having a low transmittance in the infrared region, in particular an aluminophosphate glass containing copper (II) oxide.

  Glass with low transmittance in the infrared range is used as a color correction filter in color video cameras, as a shield for illumination color displays (eg in aircraft cockbits), as a progressive filter, as a stray light filter for monochromators, as goggles Used as an inorganic component of plastic composite filters and as filter glass for CCD (Charge Coupled Device) and CMOS cameras.

  As an example, a color video camera mainly uses CCD and CMOS as solid state image sensor devices. These solid state image sensor devices generally have photosensitivity that extends to the near infrared region. For this reason, when natural light collides with the image sensor device, the formed image is reddish. Therefore, to avoid this problem, the light to be impinged on the image sensor device is first passed through an IR filter that absorbs near infrared light.

  Glass used as an IR filter should have as high a transparency as possible in the UV and visible light range (about 400-625 nm) and as low a transparency as possible in the infrared range (above 625 nm). . As a result, the glass is widely color neutral. For example, when using a video camera, it is desirable to reduce the intensity of the incident light in the> 700 nm region so that the recording redness caused by the CCD and / or CMOS is compensated.

  In addition, it is desirable for the glass to have sufficient weather resistance to ensure that the spectral transmission characteristics do not change in humid air. Furthermore, a particularly low coefficient of thermal expansion is desirable for industrial production of large surface filters. Thus, an IR absorbing glass for use as an IR filter preferably has a steep absorption edge in the near infrared range, a uniform high transmittance in the transparent range for near UV and visible light, and a low coefficient of thermal expansion. , And have good weather resistance.

Both aluminophosphate glasses containing copper (II) oxide and their use as optical glass filters are known in the art. For example, US Pat. No. 5,713,212 describes a copper (II) oxide-containing aluminophosphate glass having a sharp absorption edge, low transmittance in the near infrared range, and uniform high transmittance in the visible range. Disclose. The glass in wt% of the _{oxide-based, P 2 O 5 8-13; Al} 2 O 3 8-13; B 2 O 3 0-5.5; SiO 2 0-2.1; Li 2 O 0- 2.5; Na ₂ O 0-6; K ₂ O 0-14; Rb ₂ O 0-2.5; Cs ₂ O 0-2.5; Alkali metal oxide total 3-14; MgO 2.5- 4.9; CaO 0-2.5; SrO 0-2.5; BaO 0-2.5; ZnO 0-2.5; alkaline earth oxide + ZnO total less than 5; CuO 2-7.5; V ₂ O ₅ 0.001-0.5; and CuO + V ₂ O ₅ 2-7.5.

U.S. Pat. No. 5,750,448 describes good chemical resistance, very good devitrification stability, high transmission at wavelengths in the range of 350 to 550 nm, and 1.52 to 1.54. A copper (II) oxide-containing aminophosphate glass having a refractive index nd of 5 is disclosed. This glass is in oxide-based wt%, Al ₂ O ₃ 4-9; P ₂ O ₅ 67-75; BaO 0.5-6; CaO 0.1-1; MgO 0-4; SrO 0-1 ZnO 0.2-1; BaO + CaO + MgO + SrO + ZnO total 3.5-7; Na ₂ O 1.5-5; K ₂ O 2.5-3.5; Li ₂ O 0.5-5; Na ₂ O + K ₂ O + Li ₂ O total 5-13; SiO ₂ 0-1; B ₂ O ₃ 1-2.5; As ₂ O ₃ 0.1-0.5; F 0-1.3; CeO ₂ 0.2-0. 4; CuO 1-6; and Al ₂ O ₃ + SiO ₂ + CeO ₂ total / P ₂ O ₅ + B ₂ O ₃ = 0.06-0.125 Kg.

  See also the following references disclosing copper-containing glasses and their manufacture. U.S. Patent Nos. 6,225,244, 5,668,066, 5,242,868, 5,227,343, DE2908697, DE29272621, DE32229442, DE3414682, and DE4031469.

  The present invention provides a uniform high transmission in the visible near UV and visible transmission range, for example with a steep absorption edge and low transmission in the near infrared range, in combination with elevated temperature and high relative humidity The present invention relates to an aluminophosphate glass containing copper (II) oxide that provides excellent chemical durability under the following conditions.

  Therefore, one aspect of the present invention has a steep absorption edge in the near infrared range, a uniform high transmittance in the transparent range for near UV and visible light, a low coefficient of thermal expansion, and good weather resistance It is to provide a Cu-containing, IR-absorbing aluminophosphate glass suitable for use as an IR filter.

  According to the present invention, a Cu-containing aluminophosphate glass composition having the following composition (in wt%) is provided.

P ₂ O ₅ 65-80
Al ₂ O ₃ 4-20 (Example 4-15)
SiO ₂ 0-5
B ₂ O ₃ 0- <5.5
Y ₂ O ₃ 0-2.1
La ₂ O ₃ 0-2.1
MgO 0-7.9
CaO 0-2.5
SrO 0-2.5
BaO 0-2.5
ZnO 0-8
SR'O <18
Li ₂ O> 2-12.5
Na ₂ O 0-6
K ₂ O 0-4
Rb ₂ O 0-2.5
Cs ₂ O 0-2.5
SR " ₂ O> 2-15
SR ″ ′ ₂ O ₃ 4-24 (Example 4-20 or 4-15)
CuO 5-15 (Example 5-12%, 5-10.5%, or 5-7.5%)
V ₂ O ₅ 0-0.5
SCuO ₊ V ₂ O 5 5-15 (eg 5-12%, 5-10.5%, or 5-7.5%)

Where SR′O is the sum of ZnO and all alkaline earth metal oxides, SR ″ ₂ O is the sum of all alkali metal oxides, and SR ′ ″ ₂ O ₃ is R ′ ″ is Al , B, Y or La is the sum of all R ′ ″ ₂ O ₃ compounds.

According to a further aspect of the invention, the aluminophosphate glass further comprises CeO ₂ 0-3.0 wt%, MnO ₂ 0-3.0 wt%, and Cr ₂ O ₃ 0-0.5 wt%, wherein total CeO _2, MnO ₂ and _Cr 2 _{O 3} is> 0-0.5wt%. In addition or alternatively, according to a further aspect of the invention, the aluminophosphate glass is Sb ₂ O ₃ 0-0.3 wt%, SO ₃ 0-0.3 wt%, chlorine 0-0.5 wt%. %, Fluorine 0-10 wt% (eg 0-3 wt% or 0.05 wt%), where the sum of Sb ₂ O ₃ , SO ₃ and chlorine is> 0-0.8 wt%. The fluorine content is higher, for example 0-30 wt% or 0-20 wt%.

  According to further aspects, as color correction filters for color video cameras, as illumination color displays (eg in aircraft cockpits) as shields, as monochromator stray light filters, as progressive filters, as inorganic components of plastic composite filters, goggles Glass for use as a lens, as a filter glass for CCD and CMOS, or as a photodetector. This glass is a Cu-containing aluminophosphate glass composition having the following composition (in wt%):

P ₂ O ₅ 65-80
Al ₂ O ₃ 4-20 (Example 4-15)
SiO ₂ 0-5
B ₂ O ₃ 0- <5.5
Y ₂ O ₃ 0-2.1
La ₂ O ₃ 0-2.1
MgO 0-7.9
CaO 0-2.5
SrO 0-2.5
BaO 0-2.5
ZnO 0-8
SR'O <18
Li ₂ O> 2-12.5
Na ₂ O 0-6
K ₂ O 0-4
Rb ₂ O 0-2.5
Cs ₂ O 0-2.5
SR " ₂ O> 2-15
SR ″ ′ ₂ O ₃ 4-24 (Example 4-20 or 4-15)
CuO 5-15 (Example 5-12%, 5-10.5%, or 5-7.5%)
V ₂ O ₅ 0-0.5
SCuO ₊ V ₂ O 5 5-15 (eg 5-12%, 5-10.5%, or 5-7.5%)

Where SR′O is the sum of ZnO and all alkaline earth metal oxides, SR ″ ₂ O is the sum of all alkali metal oxides, and SR ′ ″ ₂ O ₃ is R ′ ″ is Al , B, Y or La is the sum of all R ′ ″ ₂ O ₃ compounds.

According to a further aspect of the invention, the aluminophosphate glass for use in the device further comprises CeO ₂ 0-3.0 wt%, MnO ₂ 0-3.0 wt%, and Cr ₂ O ₃ 0-0. comprises 5 wt%, wherein the total _CeO 2, MnO ₂ and _Cr 2 _{O 3} is> 0-5.5wt%. In addition or alternatively, according to a further aspect of the present invention, the aluminophosphate glass for use in the device further comprises Sb ₂ O ₃ 0-0.3 wt%, SO ₃ 0-0.3 wt%. %, Chlorine 0-0.5 wt%, and fluorine 0-10 wt% (e.g. 0-3 wt% or 0.05 wt%), the sum of Sb ₂ O ₃ , SO ₃ and chlorine is> 0-0.8 wt% It is. The fluorine content is higher, for example 0-30 wt% or 0-20 wt%.

  According to a further aspect, a method of filtering infrared light between at least one light source and at least one light receiving device, comprising Cu having the following composition (in wt%) between the light source and the light receiving device: There is provided a method comprising placing glass, whereby the glass reduces the amount of infrared light from the at least one light source impinging on the at least one light receiving device.

P ₂ O ₅ 65-80
Al ₂ O ₃ 4-20 (Example 4-15)
SiO ₂ 0-5
B ₂ O ₃ 0- <5.5
Y ₂ O ₃ 0-2.1
La ₂ O ₃ 0-2.1
MgO 0-7.9
CaO 0-2.5
SrO 0-2.5
BaO 0-2.5
ZnO 0-8
SR'O <18
Li ₂ O> 2-12.5
Na ₂ O 0-6
K ₂ O 0-4
Rb ₂ O 0-2.5
Cs ₂ O 0-2.5
SR " ₂ O> 2-15
SR ″ ′ ₂ O ₃ 4-24 (Example 4-20 or 4-15),
CuO 5-15 (Example 5-12%, 5-10.5%, or 5-7.5%)
V ₂ O ₅ 0-0.5
SCuO ₊ V ₂ O 5 5-15 (eg 5-12%, 5-10.5%, or 5-7.5%)

Where SR′O is the sum of ZnO and all alkaline earth metal oxides, SR ″ ₂ O is the sum of all alkali metal oxides, and SR ′ ″ ₂ O ₃ is R ′ ″ is Al , B, Y or La is the sum of all R ′ ″ ₂ O ₃ compounds.

According to a further aspect of the invention, the aluminophosphate glass further comprises CeO ₂ 0-3.0 wt%, MnO ₂ 0-3.0 wt%, and Cr ₂ O ₃ 0-0.5 wt%, wherein total CeO _2, MnO ₂ and _Cr 2 _{O 3} is> 0-0.5wt%. In addition or alternatively, according to a further aspect of the invention, the aluminophosphate glass is Sb ₂ O ₃ 0-0.3 wt%, SO ₃ 0-0.3 wt%, chlorine 0-0.5 wt%. %, Fluorine 0-10 wt% (eg 0-3 wt% or 0.05 wt%), where the sum of Sb ₂ O ₃ , SO ₃ and chlorine is> 0-0.8 wt%. The fluorine content is higher, for example 0-30 wt% or 0-20 wt%.

  Various other features of the present invention and the benefits associated therewith will be more fully appreciated when understood with reference to the accompanying drawings.

  The glass according to the invention has a low transmission in the infrared range and therefore as a color correction filter for color video cameras, as a shield for illumination color displays (eg in aircraft cockpits), and as a monochromator stray light It is useful as a filter, as a progressive filter, as an inorganic component of a plastic composite filter, or as goggles. The glasses of the present invention are particularly useful as filter glasses for CCD and CMOS cameras, and detectors that block IR light from reaching the detector, but at the same time pass the maximum amount of light in the visible portion of the spectrum. Useful when used as an application.

  This glass has as high a transmission as possible in the near UV and visible light range (about 450-625 nm) and as low a transparency as possible in the infrared range (about 625 nm and above). A typical desired transmission curve for the glass of the present invention is given in FIG.

  Specifically, the aluminophosphate glass according to the present invention preferably has a maximum transmittance (including reflection loss) exceeding 40% when measured in a wavelength range of 490 to 560 nm on a 1 mm thick specimen and a 1 mm thick specimen. Shows a transmittance (including reflection loss) of at least about 30% when measured at a wavelength of 600 nm and a transmittance (including reflection loss) of less than about 2% when measured at a wavelength of 700 nm with a 1 mm thick sample. .

  Further, the aluminophosphate glass according to the present invention has a maximum transmittance (including reflection loss) of> 90% when measured in a wavelength range of 495-505 nm with a 1 mm thick sample, and a wavelength with a 1 mm thick sample. It is particularly preferable to show a transmittance of 47% ± 3% (including reflection loss) when measured at 600 nm and a transmittance of less than <2% when measured at a wavelength of 700 nm with a sample having a thickness of 1 mm.

  The wavelength for maximum transmittance (when measured on a sample with a thickness of 1 mm) is preferably 480 nm-550 nm, more preferably 480 nm-520 nm, especially 490 nm-510 nm, and especially 495 nm-505 nm.

  Preferably, the transmittance at 600 nm is greater than 35%, more preferably> 40%, and preferably at 70 nm, the transmittance is less than about 2%, more preferably <1.5%.

  Thus, according to one aspect of the present invention, the aluminophosphate glass according to the present invention has a maximum transmittance (reflection loss) exceeding 40% in a wavelength range of 490-590 nm, particularly 520-560 nm, on a 1 mm thick specimen. At least about 30% transmittance (including reflection loss) when measured at a wavelength of 600 nm on a 1 mm thick specimen, and not more than about 2% at a wavelength of 700 nm, preferably about 1.5% It has transmissivity (including reflection loss) that does not exceed.

  As discussed above, the glass preferably exhibits high weather resistance that ensures that the spectral transmission properties are unchanged in humid air and when exposed to elevated temperatures. A typical test condition is to expose a glass specimen to a temperature of 60 ° C. for up to 500 hours at 90% relative humidity. The glass of the present invention is determined from visual inspection of the glass surface after exposure to these test conditions for spots, fog or film cover surface area, corrosion, or deposition of glass components that have eluted from the glass and resolidified on the glass surface. No evidence of significant chemical degradation. If this condition is satisfied, there is no significant deterioration due to deterioration of the optical quality of the film surface during transmission.

  Usually phosphate-based glasses are not known for good chemical durability. Surprisingly, however, the glass according to the invention provides a significant durability improvement. Although it is not fully understood why this glass provides improved durability for 500 hours under 60 ° C. and 90% relative humidity test conditions, it forms a highly covalent bond with oxygen. It is believed to be due to the use of glass modifiers (such as Al, Zn, Ca, Mg and Li).

The glasses according to the invention are based on phosphorus. The use of phosphorus as the basic glass-forming oxide of the glasses of the present invention leads to obtaining the desired transmission performance from the colorants doped into the glass. More common silicate type glasses do not provide an acceptable transmission curve when doped with colorants. Generally, the glass is 65 to 80 wt% (such as 68 to 78 wt%, or 71 to 78 wt%), for example, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, It has a P ₂ O ₅ content of 78 or 80 wt%. More preferably, the glass has a P ₂ O ₅ content of 68 wt% or more, more preferably 70 wt% or more, more preferably 72 wt% or more.

In addition, generally the glass is 4 to 20 wt%, preferably 4 to 15 wt% (such as 5 to 12 wt%, 4 to 14 wt%, 8 to 12 wt%), for example 4, 5, 6, 7, 8, 9, It has an Al ₂ O ₃ content of 10, 11, 12, 13 or 14 wt%. Preferably the glass has an Al ₂ O ₃ content of 5 wt% or more, more preferably 6 wt% or more, and even more preferably 8 wt% or more. This is because these glasses are characterized by improved chemical durability.

In addition, the glass can contain up to <5.5 wt% (eg 1.5 to 5 wt%), in particular 0 to 5 wt%, in particular 0 to 4 wt% B ₂ O ₃ . Glasses can also contain Y2O3 and / or La2O3 in amounts up to 2.1 wt% each.

Generally, the glass is 4 to 15 wt% (such as 6 to 14 wt%, 8 to 12 wt%, 8 to 14 wt%, or 8 to 15 wt%), for example 4, 5, 6, 7, 8, 9, 10, 11, It has a content of 12, 13, 14, or 15 wt% SR ″ ′ ₂ O _3, where SR ″ ′ ₂ O ₃ is the sum of R ″ ′ ₂ O ₃ components and R ″ ′ is Al, B, Y And La. Preferably the glass has an SR "' ₂ O ₃ content of 5 wt% or more, more preferably 6 wt% or more, more preferably more than 8 wt%, since these glasses are characterized by improved chemical durability. is there.

The alkali metal oxides used in the glass of the present invention are Na ₂ O, K ₂ O, Li ₂ O, Rb ₂ O and Cs ₂ O, preferably Na ₂ O and Li ₂ O, especially Li _2. O. The total amount of alkali metal oxides (SR ″ ₂ O, where R ″ is Na, K, Li, Rb and Cs) is> 2 to 15 wt%, for example 2,3,4,5,6,7,8, 9, 10, 11, 12, 13, 14 or 15 wt%, preferably> 2 to 10 wt%. For example, the glass has an R ″ ₂ O content of> 2 to 4.5 wt%. These additives enhance the meltability of the composition of the invention. The glass is preferably> 2 to 15 wt% (eg, 0.6- 3.8wt%, 2.1-5.5wt%, and Li ₂ O content of 2.1-5wt%), and Na ₂ O content of 0-6wt%, and _{K 2} O content of 0-4wt%, and having Rb ₂ O and Cs ₂ O content of their 0-2.5wt%.

  Alkaline earth metal oxides used in the glass of the present invention are MgO, CaO, SrO and BaO. However, ZnO can be used interchangeably with these alkaline earth metal oxides. MgO and ZnO can be used at high levels, for example MgO 0 to 7.9 wt% and ZnO 0 to 8 wt%. Overall, the sum of alkaline earth metal oxides and ZnO (SR′O, where R ′ is Mg, Ca, Sr, Ba and Zn) is <18 wt% (0-8 wt% or 0-6 wt%), for example 0 5,1,1.5,2,3,4,5,6,7,8,9,10,11,12,13,14,15 or 16 wt%. Preferably MgO and ZnO are for example 0 to 16 wt%, for example 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 Or metal oxides employed at a total level of 16 wt%, preferably 0-15 wt% and more preferably 0-10 wt%. For example, the MgO content can be 0-3 wt% (eg, 1.5-3.0 wt%) and / or the ZnO content can be 0-6 wt% (eg, 5-5.7 wt%). Most preferably, MgO is a metal oxide used at a level of> 0 to 7.9 wt%. These additive components enhance the chemical durability of the glass of the present invention.

  According to a further aspect of the invention, the BaO content of the glass is preferably <0.5 wt%, especially <0.4 wt%, and especially <0.3 wt%. According to another aspect of the invention, the CaO content is <0.1 wt% and / or the ZnO content is 5-8 wt%. According to another aspect of the invention, the MgO content is at least 2.5%, or the ZnO content is at least 5%.

The CuO content is, for example, 5 to 7.5 wt% (eg 5 to 6.5 wt%) to provide absorption in the infrared range. However, higher CuO contents are possible. Thus, the CuO content can be 5-15 wt%, such as 5-12 wt%, or 5-10.5 wt%. Furthermore, the optional addition of 0.001 to 0.5 wt% of V ₂ O ₅ affects the steepness of the absorption edge in the IR and can be very beneficial. The absorption at a high _V 2 _{O 5} content may occur in the visible range, from 0.001 to 0.1 wt% or less, _{V 2} to especially 0.001 to glass of the present invention is _V 2 _{O 5} of less 0.05 wt% Preferred when O ₅ is added. However, the total amount of CuO and V ₂ O ₅ generally does not exceed 15 wt% and preferably does not exceed 12% (eg 10.5 or 7.5 wt% or less).

For absorption in the infrared range, the presence of copper ions in the +2 valence state (eg but not in combination with the presence of +5 valent vanadium ions) is important. The glass is therefore preferably melted in an embodiment known in the art under oxidizing conditions. This can be achieved, for example, by adding nitrate to the batch. Good results are obtained by adding up to 5.5 wt% NO ₃ ions, in particular 1.5 to 5.5 wt% NO ₃ ions to the final glass. For stabilization of the oxidation step, the glass can optionally contain an oxidizing agent such as MnO ₂ , Cr ₂ O ₃ or CeO ₂ . The addition of CeO ₂ is preferred. This is because a desirable frequency of absorption in the near infrared range can be obtained by this method. CeO ₂ can be present in the glass in an amount up to 3 wt%, preferably in an amount of 0.05 to 2.5 wt%. MnO in an amount of up to 3 wt%, preferably be present in an amount up to 1 wt%, and the amount of _Cr 2 _{O 3} up to 0.5 wt%, it preferably is present in an amount of up to 0.1 wt% it can. Since Cr ₂ O ₃ generates absorption in the visible range of the spectrum, it is used only in rare cases. The total amount of the oxidizing agents CeO ₂ , MnO ₂ and Cr ₂ O ₃ does not exceed 5.5 wt%, and a total amount of 3 wt% or less, particularly 1 wt% or less is preferred.

If necessary, the glass can be clarified with conventional fining agents such as halogens such as Sb ₂ O ₃ , F or Cl, or SO ₃ . In this case, however, the clarifying agent adversely affects the equilibrium between the high and low valence states of the ions that can occur in some oxidation steps, for example in the direction of the low valences of Cu, Ce and V ions. must not. This is true when halogen (Cl or F) or Sb ₂ O ₃ is used for clarification. Therefore, the colorant, oxidizer, and clarifying agent concentrations should be adjusted to obtain optimal results, which can be routinely performed by several simple test melts.

Usually advantageous results are obtained by the use of Sb ₂ O ₃ and SO _{3 in} amounts of 0.3 wt% each and halogen (Cl, F) in amounts up to 0.5 wt%, but with the addition of clarifiers Does not exceed a total of 0.8 wt%, and usually a maximum of 0.5 wt% is sufficient.

Glass has been described as generally containing CuO alone or in combination with V ₂ O ₅ as a colorant to provide IR filtering properties, but in combination with or instead of the CuO / CuO—V ₂ O ₅ combination. Other colorants can also be used. These other colorants include Fe ₂ O ₃ , SnO ₂ , Nd ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , CoO and NiO, each used in amounts up to 2 wt%.

  The disclosures of all applications, patents and publications cited above and below are hereby incorporated by reference.

  In the following examples, all temperatures are set forth in uncorrected degrees Celsius, and all parts and percentages are by weight unless otherwise specified.

  In the glass examples discussed below, the composition is expressed in weight percent oxide and the cord system described in Table 1 is an indicator of the inspected glass surface quality after 500 hours exposure at 60 ° C. temperature and 90% relative humidity. Adopted as.

  Characterization of the glass of the present invention was performed in two series of chemical endurance tests for 500 hours at 60 ° C. and 90% relative temperature performed in a Blue M electrical model FRS-136 environmental test chamber. These characterizations are shown in Table 1.

  Preferably, the glass composition according to the invention has a code value of at most 3, in particular at most 2, in particular at most 1.

The glass of the present invention is prepared by mixing suitable amounts of each component into a batch, charging the batch into fused silica or platinum crucible, and melting by induction heating, for example from 1000 ° C. to 1500 ° C., depending on the selected composition and components. It can be manufactured conventionally. Use of fused silica crucible involves incorporation of SiO ₂ to almost always 0.2 to glass of the present invention at the level of 5 wt%. Preferably, the SiO ₂ content in the glass composition is 0 to 3 wt%. The glass can then be clarified, typically at temperatures above 1200 ° C., typically for 2 to 4 hours, with oxygen and / or nitrogen gas equi-interval and agitation, depending on the composition and hence the melt viscosity. The glass is then typically cast into a steel mold, annealed at a transition temperature plus about 20 ° C. for about 2 hours, and cooled to room temperature at 30 ° C./hour. These operations were followed in the examples in Table 2 presented below.

Glass was melted and characterized for basic optical and physical properties and curability when exposed for 500 hours at 60 ° C. temperature and 90% relative humidity. These properties are summarized in Table 3 below. In Table 3,% T relates to transmittance, Tg relates to glass transition temperature, and CTE relates to linear expansion coefficient in the indicated temperature range. The CTE value is given in units of 10 ⁻⁷ / K.

For reasons of easier manufacturability during production and higher yields (cutting, grinding and polishing), the CTE (20-300 ° C.) is preferably low. Therefore, the CTE (20-300 ° C.) of the glass of the present invention is preferably about 110 × 10 ⁻⁷ / K or less, more preferably <100 × 10 ⁻⁷ / K, preferably <90 × 10 ⁻⁷ / K. is there.

  A low Tg increases the processing time (slow cooling), so that the Tg of the glass of the present invention is preferably about 480 ° C. or less, particularly 460 ° C. or less.

  The above examples can be repeated with similar success by substituting the general or specifically described reactants and / or operating conditions of the present invention for those used in the above examples.

  From the foregoing description, those skilled in the art can readily ascertain the essential features of the present invention, and various modifications and variations of the present invention to adapt to various applications and conditions without departing from the spirit and scope thereof. Modifications can be made.

1 provides a representative desirable transmission curve for the glasses of the present invention.

Claims (40)

In wt%
P ₂ O ₅ 65-80
Al ₂ O ₃ 4-20
SiO ₂ 0-5
B ₂ O ₃ 0- <5.5
Y ₂ O ₃ 0-2.1
La ₂ O ₃ 0-2.1
MgO 0-7.9
CaO 0-2.5
SrO 0-2.5
BaO 0-2.5
ZnO 0-8
SR'O <18
Li ₂ O> 2-12.5
Na ₂ O 0-6
K ₂ O 0-4
Rb ₂ O 0-2.5
Cs ₂ O 0-2.5
SR " ₂ O> 2-15
SR "' ₂ O ₃ 4-24
CuO 5-15
V ₂ O ₅ 0-0.5
SCuO + V ₂ O ₅ 5-15
Where SR′O is the sum of ZnO and all alkaline earth metal oxides, SR ″ ₂ O is the sum of all alkali metal oxides, and SR ″ ′ ₂ O ₃ is R ″. Cu-containing aluminophosphate glass, which is the sum of all R ″ ′ ₂ O ₃ compounds where “is Al, B, Y or La.   The glass of claim 1 wherein the amount of Cu is 5-12 wt%.   The glass of claim 1, wherein the amount of Cu is 5-10.5 wt%.   The glass of claim 1 wherein the amount of Cu is 5-7.5 wt%. The glass according to claim 1, wherein the glass contains 0-0.3 wt% of Sb ₂ O ₃ . The glass or glass of claims 1 to 5 contains CeO ₂ 0-3.0wt%. The glass according to claim 1, wherein the glass contains 0 to 3.0 wt% of MnO ₂ . The glass according to claim 1, wherein the glass contains 0 to 0.5 wt% of Cr ₂ O ₃ . The glass according to claim 1, wherein the total amount of CeO ₂ , MnO ₂ and Cr ₂ O _{3 in} the glass is> 0-5.5 wt%. The glass according to claim 1, wherein the glass contains 0-0.3 wt% SO ₂ .   The glass according to claim 1, wherein the glass contains 0-0.5 wt% of chlorine. Sb ₂ O _3, the total amount of SO ₂ and chlorine> a claims 1 to 0-0.8Wt% to 11 either glass.   The glass according to claim 1, wherein the glass contains 0-10 wt% fluorine. Either glass P ₂ O ₅ content of claims 1 is 68-78wt% 13. P ₂ O ₅ content of the glass of claim 14 which is 71-78wt%. The glass according to claim 1, wherein the Al ₂ O ₃ content is 4-14 wt%. Al ₂ O ₃ content of the glass of claim 16 which is 5-12wt%. The glass according to any one of claims 1 to 17, wherein the content of B ₂ O ₃ is 0-5 wt%. The glass according to claim 1, wherein the Y ₂ O ₃ content is 0-2.1 wt% and the La ₂ O ₃ content is 0-2.1 wt%. Either glass li ₂ O content claims 1 is 2.1-5.5wt% 19. Glass according to claim 20 li ₂ O content is 2.1-5wt%.   The glass according to any one of claims 1 to 20, wherein the SR'O content is 0-8 wt%.   The glass of claim 22, wherein the SR'O content is 2-6 wt%.   24. A glass according to claim 1, wherein the MgO content is 1.5-3.0 wt%.   The glass according to any one of claims 1 to 24, wherein the ZnO content is 5-5.7 wt%. The glass according to claim 1, wherein the Al ₂ O ₃ content is 4-15 wt% and the SR ″ ′ ₂ O ₃ content is 4-20 wt%. 27. The glass according to claim 1, wherein the SR ″ ′ ₂ O ₃ content is 4 to 15 wt%. The glass according to claim 1, wherein the SR ″ ′ ₂ O ₃ content is 6-14 wt%. Glass of claim 28 SR "_'2 O ₃ content is 8-12wt%. Glass of claim 28 SR "_'2 O ₃ content is 8-14wt%. SR "_'2 O ₃ content is one of the glass of claims 1 is 8-15wt% 27. Essentially wt%,
P ₂ O ₅ 74.6
Al ₂ O ₃ 8.1
ZnO 5.3
Li ₂ O 2.78
Na ₂ O 0.4
ZrO ₂ 3.5
CuO 5.5
Sb ₂ O ₃ 0.1
A Cu (II) -containing aluminophosphate glass.   The glass has a maximum transmittance including reflection loss exceeding 40% in the wavelength range of 490 to 560 nm as measured with a 1 mm thick sample; and at least 30% at a wavelength of 600 nm measured with a 1 mm thick sample. The glass of claim 1 exhibiting a transmittance of less than 2% at a wavelength of 700 nm as measured on a 1 mm thick specimen;   The glass contains> 90% reflection loss in the wavelength range of 495 to 505 nm, measured with a 1 mm thick sample, and has a maximum transmission; 47% at a wavelength of 600 nm measured with a 1 mm thick sample A transmittance of ± 3%, including reflection loss; and a transmittance, including reflection loss, of no more than <2% at a wavelength of 700 nm as measured on a 1 mm thick specimen. Glass.   The glass of claim 1, wherein the glass exhibits a maximum transmission wavelength of 480 nm to 520 nm when measured on a 1 mm thick sample.   The glass of claim 1, wherein the glass exhibits a transmittance of> 40% at 600 nm and a transmittance of <1.5% at 700 nm.   37. A method of providing color correction for a color video camera, comprising using the glass of any of claims 1-36 as a color correction filter for the color video camera.   37. A shielding method for an illumination color display, comprising using the glass of any of claims 1 to 36 as a shield for the illumination color display.   A method of filtering stray light, comprising using the glass according to any one of claims 1 to 36 as a stray light filter.   37. A method of filtering infrared light between at least one light source and at least one light receiving device comprising disposing the glass of any of claims 1-36 between the light source and the light receiving device. Method.

Images