Glass, near-infrared absorption cut-off filter, and solid-state imaging element

Abstract

The present invention relates to a glass containing, in mol% based on oxides, 25% or more of P2O5 and 0.5% or more in total of near-infrared absorbing components, wherein the ratio represented by {[H+ A] / [H+ B]} of the H+ concentration [H+ A] on the surface of the glass and the H+ concentration [H+ B] at a depth of 100 μm from the surface of the glass is 2 or less.

Description

Glass, near-infrared absorption cut filter and solid-state imaging device

[0001] The present invention relates to a glass, a near-infrared absorption cut filter, and a solid-state imaging device.

[0002] Visibility correction filters are used in imaging devices that use solid-state imaging elements such as CCDs (Charge Coupled Devices) and are installed in cameras such as mobile devices, personal computers, and single-lens reflex cameras. These visibility correction filters enable the colors in photographs to be closer to the visibility of humans.

[0003] The visibility correction filter, which is also called a near-infrared absorbing filter, is required to have spectral characteristics of absorbing light in the near-infrared region and transmitting light in the visible region. Therefore, the glass used for the near-infrared absorbing cut filter often contains Cu ions to absorb light in the near-infrared region.

[0004] Common examples of such glass include phosphate glass and fluorophosphate glass, with phosphate glass tending to have superior spectral characteristics. However, phosphate glass is prone to reacting with water, deteriorating under high temperature and humidity conditions, and exhibiting poor weather resistance. As a result, the film formed on the main surface of the glass is prone to peeling, leading to deterioration of the element. This occurs because the P-O-P bonds contained in the phosphate glass are hydrolyzed by water molecules, causing the released phosphoric acid to float to the surface of the glass.

[0005] In contrast, in Non-Patent Document 1, Al is added to phosphate glass. ２ O ３ It is disclosed that the addition of a stronger three-dimensional network structure is formed, improving weather resistance.

[0006] N. J. Kreidl and W. A. Weyl, J. Am. Ceram. Soc. , 24:372-378 (1941)

[0007] However, the glass contains Al ２ O ３Addition of aluminum phosphate reduces the solubility and makes it more likely that devitrification will occur due to aluminum phosphate. If the melting temperature of the glass is increased to prevent the devitrification, the light transmittance in the visible region will decrease. This is thought to be due to a change in the valence of the near-infrared absorbing component, such as some of the divalent Cu ions present to absorb light in the near-infrared region becoming monovalent. Therefore, when Al is added to the glass, ２ O ３ It is not appropriate to add too much.

[0008] Therefore, an object of the present invention is to provide a new glass, such as phosphate glass or fluorophosphate glass, which contains phosphorus and a near-infrared absorbing component and has improved weather resistance, as well as a near-infrared absorption cut filter and a solid-state imaging device made of the glass.

[0009] As a result of intensive research by the present inventors, it was found that the glass containing phosphorus and a near-infrared absorbing component has a high H ＋ concentration and H at a depth of 100 μm from the surface of the glass ＋ The inventors have found that the above problems can be solved by controlling the concentration ratio, and have thus completed the present invention.

[0010] That is, the present invention relates to the following [1] to

[14] . [1] In mole % on an oxide basis, P ２ O ５ and a total of 0.5% or more of near-infrared absorbing components, ＋ Concentration [H ＋ Ａ ] and H at a depth of 100 μm from the surface of the glass ＋ Concentration [H ＋ Ｂ ] with {[H ＋ Ａ ] / [H ＋ Ｂ ]} is 2 or less. [2] A glass having a β-OH value of 1 mm －１ The glass according to the above [1], wherein the {[H ＋ Ａ ] / [H ＋ Ｂ]} is less than 1. [4] The glass according to any one of [1] to [3] above, having a transmittance of 70% or more at a wavelength of 550 nm when converted into a glass having a thickness of 0.2 mm. [5] The glass according to any one of [1] to [4] above, having a transmittance of 30% or less at a wavelength of 800 nm when converted into a glass having a thickness of 0.2 mm. [6] The glass according to any one of [1] to [5] above, containing one or more elements selected from the group consisting of Cu, Fe, and V as the near-infrared absorbing component. [7] The glass according to any one of [1] to [6] above, containing Cu as the near-infrared absorbing component, and containing 0.5% or more of CuO, expressed in mole % on an oxide basis. [8] The glass according to any one of [1] to [7] above, containing one or more elements selected from the group consisting of Ti, W, and Nb. [9] The glass according to any one of [1] to [7] above, containing, in mole % on an oxide basis, TiO ２ , W.O. ３ and Nb ２ O ５

[10] The glass according to [8] above, containing 5% or more in total of P.

[11] The glass according to [8] above, containing 5% or more in total of P, expressed in mole percent on an oxide basis. ２ O ５ :25~80%, Al ２ O ３ : 1 to 20%, ΣR ２ O: 0 to 35% (wherein R represents Li, Na, K, Rb, and Cs), ΣR′O: 0 to 30% (wherein R′ represents Mg, Ca, Sr, Ba, and Zn), and CuO: 0.5 to 30%, ２ O is Li ２ O, Na ２ O.K. ２ O, Cs ２ O and Rb ２

[11] The glass according to any one of the above [1] to [9], wherein the content in mole percent on an oxide basis is: P ２ O ５ :30~50%, Al ２ O ３ : 1 to 10%, ΣR ２O: 10 to 35% (wherein R represents Li, Na, K, Rb, and Cs), ΣR′O: 0 to 10% (wherein R′ represents Mg, Ca, Sr, Ba, and Zn), CuO: 1 to 15%, TiO ２ : 0-10%, WO ３ : 0 to 10%, and Nb ２ O ５ : Satisfies 0 to 10%; ２ O is Li ２ O, Na ２ O.K. ２ O, Cs ２ O and Rb ２ The glass according to any one of the above [1] to

[10] , wherein ΣR′O means the total content of MgO, CaO, SrO, BaO, and ZnO, and the ΣR′O means the total content of MgO, CaO, SrO, BaO, and ZnO.

[12] The glass according to any one of the above [1] to

[11] , wherein the content of F, expressed in mol%, is 7% or less, in terms of an external proportion.

[13] A near-infrared absorption cut filter made of the glass according to any one of the above [1] to

[12] .

[14] A solid-state imaging device comprising the near-infrared absorption cut filter according to the above

[13] .

[0011] According to the present invention, a new glass having improved weather resistance can be obtained. ＋ concentration and H at a depth of 100 μm from the surface of the glass ＋ By controlling the ratio of the concentration, the weather resistance can be improved, and as a result, a suitable near-infrared absorption cut filter having excellent weather resistance and a solid-state imaging device including the near-infrared absorption cut filter can be provided.

[0012] The present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be modified as desired without departing from the spirit of the present invention. Furthermore, the term "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower and upper limits.

[0013] <<Glass>> The glass according to this embodiment contains, in mole percent on an oxide basis, P ２ O ５and a total of 0.5% or more of near-infrared absorbing components. ＋ Concentration [H ＋ Ａ ] and H at a depth of 100 μm from the surface of the glass ＋ Concentration [H ＋ Ｂ ] with {[H ＋ Ａ ] / [H ＋ Ｂ ]} is equal to or less than 2.

[0014] <Physical properties> Glass containing phosphorus and near-infrared absorbing components is treated with Al to improve its weather resistance. ２ O ３ When an excessive amount of Cu is added and the melting temperature of the glass is increased to prevent devitrification, the light transmittance in the visible region decreases. This is thought to be due to a change in the valence of the near-infrared absorbing component, such as a change from some of the divalent Cu ions present to absorb light in the near-infrared region to monovalent Cu ions.

[0015] Therefore, the present inventors have ２ O ３ In addition to the addition of phosphorus and a near-infrared absorbing component, investigations were conducted to improve the weather resistance of glass containing phosphorus and a near-infrared absorbing component, and the results were as follows: ＋ Ａ ] / [H ＋ Ｂ The inventors have found that the weather resistance of the glass is improved by adjusting the ratio represented by {x,y,y} to 2 or less.

[0016] The reason for this is unclear, but it is thought to be as follows: H on the glass surface ＋ Concentration [H ＋ Ａ ] at a depth of 100 μm from the surface of the glass ＋ Concentration [H ＋ Ｂ ], the P-O-P bonds in the glass increase, and the glass network becomes stronger. ２The penetration and diffusion of oxygen (O) can be suppressed. This is due to the reduction in the number of terminal phosphate groups (P—OH). As a result, the weather resistance of the glass is improved, and it is believed that the glass will be suitable for use as, for example, a near-infrared absorption cut filter.

[0017] The inventors have found that {[H ＋ Ａ ] / [H ＋ Ｂ In addition, we have discovered a glass having a novel composition as described below, in which the ratio represented by {[H ＋ Ａ ] / [H ＋ Ｂ ]} exceeds 2, the above ratio can be reduced to 2 or less by carrying out post-treatment, thereby improving weather resistance.

[0018] Further investigation by the present inventors has revealed that the above {[H ＋ Ａ ] / [H ＋ Ｂ It has been found that by making the ratio represented by {} less than 1, it is possible to improve the transmittance of visible light in addition to the weather resistance. ＋ Concentration [H ＋ Ａ ] becomes smaller, and Cu, which is a high-valence ion, is added for charge compensation. ２＋ Components that contribute to the absorption of light in the near-infrared region, such as Cu, which is an ion on the low valence side, are more likely to exist. ＋ This is thought to be due to a decrease in the proportion of components that contribute to absorption in the visible range, such as Cu, etc. In the glass according to this embodiment, the decrease in transmittance in the near-infrared range and the increase in transmittance in the visible range due to this change in the valence of Cu ions are particularly important phenomena, and this makes the glass according to this embodiment suitable for use as a near-infrared absorption cut filter.

[0019] From the above viewpoint, the glass according to this embodiment has a {[H ＋ Ａ ] / [H ＋ ＢThe ratio represented by {[H ＋ Ａ ] / [H ＋ Ｂ The lower limit of the ratio {} is not particularly limited, but is, for example, 0.01 or more.

[0020] In this specification, [H ＋ Ａ ], [H ＋ Ｂ The value of [H] is determined by secondary ion mass spectrometry (SIMS). Specifically, the value of [H] is determined by using SIMS to a depth of at least 20 μm from the surface of the glass. ＋ The H concentration (cps) on the surface of the glass was measured. The curve obtained from the surface to a depth of 20 μm was then approximated by a sigmoid curve. ＋ Concentration [H ＋ Ａ ] (cps) and H at a depth of 100 μm from the surface of the glass ＋ Concentration [H ＋ Ｂ By using this measurement method, even if the actual glass thickness is less than 100 μm, [H ＋ Ｂ ] is required.

[0021] The specific measurement conditions for SIMS are as follows: [SIMS measurement conditions] Apparatus: ADEPT1010 manufactured by ULVAC-PHI, Inc. Primary ion species: Cs+ Primary ion acceleration voltage: 5 kV Primary ion current value: 500 nA Primary ion incident angle: 60° with respect to the normal to the sample surface Primary ion raster size: 300 × 300 μm ２ Secondary ion polarity: negative Secondary ion detection area: 60 x 60 μm ２(4% of the primary ion raster size) ESA Input Lens: 0 Use of neutralization gun: Yes Method for converting the horizontal axis from sputtering time to depth: The depth of the analyzed crater is measured using a stylus surface profiler (Dektak150, manufactured by Veeco) to determine the primary ion sputtering rate. This sputtering rate is used to convert the horizontal axis from sputtering time to depth. Field Axis Potential during 1H-detection: The optimal value may vary depending on the device. The operator should carefully set the value so that the background is sufficiently removed.

[0022] From the viewpoint of further improving the weather resistance of the glass, the β-OH value of the glass according to this embodiment is set to 1 mm －１ Preferably less than 0.8 mm －１ More preferably, 0.5 mm or less －１ More preferably, 0.25 mm or less －１ The lower limit of the β-OH value is not particularly limited, but is, for example, 0.01 mm －１ The β-OH value in this specification correlates with the amount of water in the glass, and is determined by Fourier transform infrared spectroscopy (FT-IR) at 3550 cm －１ It can be calculated by dividing the absorbance at 3650 cm by the thickness of the glass. －１ ~4000cm －１ The maximum transmittance at T ０ , 3550 cm －１ The transmittance at T １ When the thickness of the glass is d (mm), the β-OH value is expressed by the following formula: β-OH value = -(1 / d) (log １０ (T １ / T ０ ))

[0023] When used as a near-infrared absorption cut filter, the glass according to this embodiment is required to have high transmittance for light in the visible range as a spectral characteristic. Therefore, the transmittance of the glass at a wavelength of 550 nm is preferably 70% or more, more preferably 75% or more, even more preferably 80% or more, and even more preferably 85% or more. The transmittance is preferably closer to 100%, but is usually 92% or less. In this specification, the transmittance of the glass is the external transmittance, including reflection losses on the front and back surfaces.

[0024] The transmittance in this specification is the transmittance converted when the glass thickness is 0.2 mm. The conversion can be performed using the following formula: T ｉ２ =T ｉ１ ｔ２／ｔ１ In the above formula, T ｉ１ is the internal transmittance of the measurement sample (transmittance excluding reflection loss on the front and back surfaces), and T ｉ２ is the internal transmittance after conversion, t1 is the thickness (mm) of the measurement sample, and t2 is the thickness to be converted, i.e., 0.2 mm in this specification. The conversion from transmittance to internal transmittance is performed using the following formula, assuming that the reflection loss R on the front and back surfaces of the glass is 0.0454: Internal transmittance = External transmittance / {100 × (1 - R) ２}

[0025] The glass according to this embodiment is required to have high absorbance of light in the near-infrared region when used as a near-infrared absorption cut filter. Therefore, the transmittance of the glass at a wavelength of 800 nm is preferably 30% or less, more preferably 25% or less, even more preferably 20% or less, even more preferably 15% or less, and most preferably 10% or less. The transmittance is preferably as close to 0% as possible, but is usually 0.01% or more.

[0026] The thickness of the glass according to this embodiment is preferably 0.03 to 1 mm. From the viewpoint of obtaining strength sufficient to prevent breakage during manufacturing, transportation, incorporation into a solid-state imaging element, etc., the thickness is preferably 0.03 mm or more, more preferably 0.05 mm or more, even more preferably 0.07 mm or more, and particularly preferably 0.1 mm or more. Furthermore, from the viewpoint of responding to the miniaturization and thinning of devices and equipment incorporating the glass, such as solid-state imaging elements, the thickness is preferably 1 mm or less, more preferably 0.8 mm or less, even more preferably 0.6 mm or less, particularly preferably 0.4 mm or less, and most preferably 0.3 mm or less.

[0027] The glass transition temperature (Tg) of the glass according to this embodiment is preferably 350 to 600° C. Here, from the viewpoint of enhancing the stability of the glass, the glass transition temperature is preferably 350° C. or higher, more preferably 375° C. or higher, even more preferably 400° C. or higher, and even more preferably 425° C. or higher. Furthermore, from the viewpoint of suppressing an increase in the melting temperature of the glass, the glass transition temperature is preferably 600° C. or lower, more preferably 575° C. or lower, even more preferably 550° C. or lower, even more preferably 525° C. or lower, and even more preferably 500° C. or lower.

[0028] <Composition> In the glass according to this embodiment, phosphorus (P) is a network-forming component and a main component necessary for vitrification. It is also a component that enhances the absorption of light in the near-infrared region. The P content in the glass, expressed as mole percent on an oxide basis, is ２ O ５ The content of P is 25% or more, preferably 25 to 80%, and more preferably 30 to 50%. ２ O ５ The content of P is preferably 25% or more, more preferably 28% or more, even more preferably 30% or more, even more preferably 35% or more, particularly preferably 40% or more, and even more preferably 45% or more. ２ O ５The content is preferably 80% or less, more preferably 75% or less, even more preferably 70% or less, even more preferably 65% ​​or less, even more preferably 60% or less, and particularly preferably 50% or less.

[0029] The glass according to this embodiment contains a component that absorbs light in the near-infrared region, i.e., a near-infrared absorbing component, so that it can be suitably used as a near-infrared absorption cut filter, etc. Here, the near-infrared absorbing component is a component whose maximum absorption wavelength is in the range of 700 to 1200 nm.

[0030] The total content of the near-infrared absorbing components, expressed in mole percent on an oxide basis, is 0.5% or more, preferably 0.5 to 30%. From the viewpoint of enhancing the absorbency of light in the near-infrared region, the total content is preferably 0.5% or more, more preferably 1% or more, even more preferably 5% or more, and even more preferably 10% or more. From the viewpoint of preventing the precipitation of devitrification inclusions in the glass, the total content is preferably 30% or less, more preferably 26% or less, even more preferably 22% or less, and even more preferably 18% or less.

[0031] Examples of near-infrared absorbing components include Cu, Fe, and V, and one of these may be used alone or two or more of them may be used in combination. That is, the glass according to this embodiment preferably contains one or more near-infrared absorbing components selected from the group consisting of Cu, Fe, and V, and more preferably contains at least Cu from the viewpoint of efficiently absorbing light in the near-infrared region.

[0032] When the glass according to this embodiment contains Cu as a near-infrared absorbing component, the CuO content, expressed in mole percent on an oxide basis, is preferably 0.5% or more, and more preferably 0.5 to 30%. From the viewpoint of efficiently absorbing light in the near-infrared region and enhancing the strength and stability of the glass, the CuO content is preferably 0.5% or more, more preferably 1% or more, even more preferably 5% or more, and even more preferably 10% or more. Furthermore, from the viewpoint of suppressing a decrease in the visible transmittance of the glass, the CuO content is preferably 30% or less, more preferably 26% or less, even more preferably 22% or less, and even more preferably 18% or less.

[0033] The glass according to this embodiment can be used in the form of a glass having a composition that allows it to be easily oxidized without post-treatment. ＋ Ａ ] / [H ＋ Ｂ ]} will be 2 or less, but without post-treatment, the ratio may not be 2 or less. Even in such a case, the ratio can be made 2 or less by the post-treatment. Furthermore, even in a composition in which the ratio is 2 or less without post-treatment, the ratio can be made smaller by the post-treatment.

[0034] From the viewpoint of more easily obtaining the effects of the post-treatment, the glass according to this embodiment preferably contains one or more elements selected from the group consisting of Ti, W, and Nb. In this case, in terms of mole % on an oxide basis, TiO ２ , W.O. ３ and Nb ２ O ５ The total content is preferably 5% or more, and more preferably 5 to 30%. From the viewpoint of more easily obtaining the effects of the post-treatment, the total content is preferably 5% or more, more preferably 7.5% or more, even more preferably 10% or more, and even more preferably 12.5% ​​or more. Furthermore, from the viewpoint of suppressing a decrease in the visible transmittance of the glass, the total content is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less.

[0035] More specifically, the composition of the glass according to this embodiment preferably satisfies the following content in mole percent on an oxide basis: ２ O ５ :25~80%, Al ２ O ３ : 1 to 20%, ΣR ２ O: 0 to 35% (where R represents Li, Na, K, Rb, and Cs), ΣR′O: 0 to 30% (where R′ represents Mg, Ca, Sr, Ba, and Zn), and CuO: 0.5 to 30%. ２ O is Li ２ O, Na ２ O.K. ２ O, Cs ２ O and Rb２ The above ΣR′O means the total content of MgO, CaO, SrO, BaO, and ZnO.

[0036] In particular, regardless of whether post-processing is performed or not, ＋ Ａ ] / [H ＋ Ｂ In the case where the glass has a composition in which the ratio represented by {P / P} is 2 or less, the content in mole % on an oxide basis preferably satisfies the following: ２ O ５ :30~50%, Al ２ O ３ : 1 to 10%, ΣR ２ O: 10 to 35% (wherein R represents Li, Na, K, Rb, and Cs), ΣR′O: 0 to 10% (wherein R′ represents Mg, Ca, Sr, Ba, and Zn), CuO: 1 to 15%, TiO ２ : 0-10%, WO ３ : 0 to 10%, and Nb ２ O ５ : Satisfies 0 to 10%. ２ O is Li ２ O, Na ２ O.K. ２ O, Cs ２ O and Rb ２ The above ΣR′O means the total content of MgO, CaO, SrO, BaO, and ZnO.

[0037] P ２ O ５ , CuO, which is one embodiment of the near-infrared absorbing component, and TiO ２ , W.O. ３ and Nb ２ O ５ The total of is as described above. The other components are explained below.

[0038] Al ２ O ３ is a component for improving weather resistance. ２ O ３The content of Al is preferably 1 to 20 mol %, more preferably 1 to 10 mol %. ２ O ３ The content of Al is preferably 1 mol % or more, more preferably 2 mol % or more, and even more preferably 3 mol % or more. In addition, from the viewpoint of suppressing a decrease in absorbency in the near-infrared region and a decrease in transmittance of light in the visible region, which are caused by an excessively high melting temperature during glass production, Al is preferably 1 mol % or more, more preferably 2 mol % or more, and even more preferably 3 mol % or more. ２ O ３ The content is preferably 20 mol % or less, more preferably 17 mol % or less, even more preferably 15 mol % or less, and even more preferably 10 mol % or less.

[0039] R ２ O is a component that lowers the melting temperature of the glass. R represents Li, Na, K, Rb, and Cs. ΣR ２ O is Li ２ O, Na ２ O.K. ２ O, Rb ２ O, and Cs ２ means the total amount of O. ２ O is preferably 0 to 35 mol %, more preferably 10 to 35 mol %. ２ From the viewpoint of preferably obtaining the above-mentioned effect of O, R ２ ΣR when O is contained ２ O is preferably 10 mol % or more, more preferably 12 mol % or more, and even more preferably 14 mol % or more. ２ The O content is preferably 35 mol % or less, more preferably 33 mol % or less, and even more preferably 32 mol % or less.

[0040] R ２ Li as O ２ O, Na ２ O and K ２ It is preferable that the compound contains at least one selected from the group consisting of Li, ２ O and Na ２ It is more preferable that the compound contains at least one of Li and O. ２ It is more preferable that the compound contains O. ２ O and Na ２It is further preferred that O is contained.

[0041] R ２ Li as O ２ When O is contained, Li ２ The content of O is preferably 0.1 to 15 mol %. ２ From the viewpoint of preferably obtaining the above-mentioned effect of O, Li ２ When O is contained, the content is preferably 0.1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and even more preferably 6 mol% or more. ２ The O content is preferably 15 mol % or less, more preferably 14 mol % or less, even more preferably 13 mol % or less, and even more preferably 12 mol % or less.

[0042] R ２ Na as O ２ If it contains O, Na ２ The content of O is preferably 0.1 to 30 mol %. ２ From the viewpoint of obtaining the above-mentioned effect of O, Na ２ When O is contained, the content is preferably 0.1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and even more preferably 15 mol% or more. ２ The O content is preferably 30 mol % or less, more preferably 28 mol % or less, even more preferably 26 mol % or less, and even more preferably 24 mol % or less.

[0043] R ２ O as K ２ If O is contained, K ２ The content of O is preferably 0.1 to 20 mol %. ２ From the viewpoint of preferably obtaining the above-mentioned effect of O, K ２ When O is contained, the content is preferably 0.1 mol% or more, more preferably 4 mol% or more, further preferably 8 mol% or more, and even more preferably 10 mol% or more. ２The O content is preferably 20 mol % or less, more preferably 18 mol % or less, even more preferably 16 mol % or less, and even more preferably 14 mol % or less.

[0044] R'O is a component for increasing the stability of the glass and lowering the melting temperature of the glass. R' represents Mg, Ca, Sr, Ba, and Zn, and ΣR'O represents the total amount of MgO, CaO, SrO, BaO, and ZnO. ΣR'O is preferably 0 to 30 mol%, and more preferably 0 to 10 mol%. Here, from the viewpoint of suitably obtaining the above-mentioned effects of R'O, when R'O is contained, ΣR'O is preferably 2 mol% or more, more preferably 4 mol% or more, and even more preferably 6 mol% or more. Furthermore, from the viewpoint of suppressing glass instability, ΣR'O is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.

[0045] Among R'O, MgO, CaO, and SrO are components that have the effect of increasing the stability of the glass, but also reduce the absorbency of light in the near-infrared region. The total content of these components is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less, and they may not be contained at all.

[0046] Among R'O, BaO has the effect of lowering the melting temperature of the glass, but is also a component that destabilizes the glass and reduces the absorbency of light in the near-infrared region. The BaO content is preferably 0 to 20 mol%. Here, from the viewpoint of suitably lowering the melting temperature of the glass, the BaO content is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. Furthermore, from the viewpoint of preventing the glass from becoming unstable, the BaO content is preferably 20 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less, and may not be contained.

[0047] Among R'O, ZnO has the effect of lowering the melting temperature of glass, but is also a component that reduces the solubility of glass. The ZnO content is preferably 0 to 20 mol%. Here, from the viewpoint of suitably lowering the melting temperature of glass, the ZnO content is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more. Furthermore, from the viewpoint of maintaining the solubility of glass, the BaO content is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less.

[0048] The glass according to this embodiment preferably contains CuO as a near-infrared absorbing component, but may contain a near-infrared absorbing component other than CuO. For example, Fe ２ O ３ , V ２ O ５ and the like. The total content of the near-infrared absorbing components including CuO is preferably 0.5 to 30 mol%. Here, from the viewpoint of increasing the absorbency of light in the near-infrared region, the total content is preferably 0.5 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, and even more preferably 10 mol% or more. Furthermore, from the viewpoint of suppressing a decrease in light transmittance in the visible region, the total content is preferably 30 mol% or less, more preferably 27 mol% or less, even more preferably 25 mol% or less, and even more preferably 23 mol% or less.

[0049] As a near-infrared absorbing component other than CuO, Fe ２ O ３ The content of Fe is preferably 0.5 to 30 mol %. ２ O ３ The content of is preferably 0.5 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, and even more preferably 10 mol% or more. ３＋ From the viewpoint of suppressing a decrease in light transmittance in the visible range due to an increase in the proportion of Fe ２ O ３The content of is preferably 30 mol% or less, more preferably 27 mol% or less, even more preferably 25 mol% or less, and even more preferably 23 mol% or less. From the viewpoint of efficiently increasing the absorbency of light in the near-infrared region, the content of CuO, which is a near-infrared absorbing component, is preferably Fe ２ O ３ and V ２ O ５ It is preferable that the content of Fe is higher than the content of at least one of ２ O ３ and V ２ O ５ It is more preferable that the content of both of these is higher than that of the other two.

[0050] In addition to the above, the glass according to this embodiment contains TiO ２ , W.O. ３ and Nb ２ O ５ The compound containing one or more selected from the group consisting of {[H ＋ Ａ ] / [H ＋ Ｂ This is preferable from the viewpoint of suitably obtaining the effect of reducing the ratio represented by {}.

[0051] TiO ２ The content of TiO is preferably 0 to 10 mol %. ２ The content of TiO is more preferably 1 mol % or more, further preferably 2 mol % or more, and even more preferably 3 mol % or more. ２ The content is preferably 10 mol % or less, more preferably 9 mol % or less, even more preferably 8 mol % or less, and even more preferably 7 mol % or less.

[0052] WO ３ The content of WO is preferably 0 to 10 mol %. ３ The content of WO is more preferably 1 mol % or more, further preferably 2 mol % or more, and even more preferably 3 mol % or more. ３The content is preferably 10 mol % or less, more preferably 9 mol % or less, even more preferably 8 mol % or less, and even more preferably 7 mol % or less.

[0053] Nb ２ O ５ The content of Nb is preferably 0 to 10 mol %. ２ O ５ The content of Nb is more preferably 1 mol % or more, even more preferably 2 mol % or more, and even more preferably 3 mol % or more. ２ O ５ The content is preferably 10 mol % or less, more preferably 9 mol % or less, even more preferably 8 mol % or less, and even more preferably 7 mol % or less.

[0054] The glass according to this embodiment is P ２ O ５ In addition, B ２ O ３ and SiO ２ The glass may contain a glass network forming component such as ２ O ５ , B ２ O ３ and SiO ２ The total content is preferably 25 to 90 mol%. From the viewpoint of suppressing a decrease in the strength of the glass, the total content is more preferably 30 mol% or more, even more preferably 35 mol% or more, and even more preferably 40 mol% or more. From the viewpoint of suppressing an increase in the melting temperature of the glass, the total content is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and even more preferably 60 mol% or less.

[0055] B ２ O ３ The content of B is preferably 0 to 30 mol %. ２ O ３ The content of B is more preferably 1 mol % or more, further preferably 5 mol % or more, and even more preferably 10 mol % or more. ２ O３ The content is preferably 30 mol % or less, more preferably 25 mol % or less, even more preferably 20 mol % or less, and even more preferably 15 mol % or less.

[0056] SiO ２ The content of is preferably 0 to 30 mol %. From the viewpoint of improving the weather resistance of the glass, SiO ２ The content of SiO is more preferably 0.5 mol % or more, further preferably 1 mol % or more, and even more preferably 2 mol % or more. ２ The content is preferably 30 mol % or less, more preferably 25 mol % or less, even more preferably 20 mol % or less, and even more preferably 15 mol % or less, and may not be contained.

[0057] The glass according to this embodiment may be a glass containing fluoride, which is called fluorophosphate glass among phosphate glasses. Fluorophosphate glass exhibits high weather resistance due to the inclusion of fluoride. However, when the glass has the same composition, the glass may have a low fluoride content. ＋ Ａ ] / [H ＋ Ｂ By adjusting the ratio {represented by} from more than 2 to 2 or less, the weather resistance is further improved. As described above, fluorophosphate glass is a glass that is inherently highly weather resistant. Therefore, the degree of improvement in weather resistance achieved by adjusting the ratio to 2 or less is remarkable in the case of glass that does not contain fluoride. Furthermore, even in the case of glass that contains fluoride but whose content is so small that it does not contribute to improving weather resistance, the degree of improvement in weather resistance achieved by adjusting the ratio to 2 or less is remarkable.

[0058] From the above viewpoint and from the viewpoint of environmental conservation, the content of F in the glass according to this embodiment, expressed as mol%, is preferably 7% or less, more preferably 5% or less, even more preferably 3% or less, even more preferably 2% or less, particularly preferably 1% or less, and may not be contained at all. Note that the content of F in the glass according to this embodiment is expressed as an exclusive percentage and is not included in the total content of glass components expressed on an oxide basis. In other words, the exclusive percentage means the content of F when the glass composition other than F contained in the glass is taken as 100 mol%.

[0059] In addition to the above components, the glass according to this embodiment may contain other components within the range that does not impair the effects of the present invention. Examples of other components include GeO ２ , ZrO ２ , SnO ２ , CeO ２ , Y ２ O ３ , La ２ O ３ , Gd ２ O ３ , Yb ２ O ３ etc. When these other components are contained, the total content is preferably 0 to 5 mol%. Here, from the viewpoint of preferably obtaining the effects of the other components, the total content is more preferably 0.1 mol% or more, and even more preferably 0.2 mol% or more. Furthermore, from the viewpoint of suppressing deterioration of absorbency of light in the near-infrared region, the total content is preferably 5 mol% or less, more preferably 4 mol% or less, and even more preferably 3 mol% or less.

[0060] The glass according to this embodiment contains PbO, As ２ O ３ , and GdF ３ It is preferable that the glass does not substantially contain any of the above. PbO is a component that reduces the viscosity of the glass and improves the manufacturing workability. ２ O ３ is a component that acts as an excellent fining agent that can generate fining gas over a wide temperature range. ２ O ３Both of these are environmentally hazardous substances, so it is preferable to avoid their inclusion as much as possible. ３ Although these are components that stabilize the glass, the raw materials for these components are relatively expensive, which leads to increased costs, and therefore it is preferable to avoid their inclusion as much as possible. Regarding the above three components, "substantially not containing" means that they are not intentionally used as raw materials, and that the content of each component in the glass is 0.1 mol % or less.

[0061] <<Near-infrared absorption cut filter>> The near-infrared absorption cut filter according to this embodiment includes the glass described above in <<Glass>>. Preferred aspects of this glass are also the same as the preferred aspects described above in <<Glass>>.

[0062] The near-infrared absorption cut filter according to this embodiment may have an optical multilayer film provided on at least one main surface of glass formed into a predetermined shape. Examples of the optical multilayer film include an IR cut film, a UV / IR cut film (a film that reflects ultraviolet and near-infrared rays), a UV cut film, and an anti-reflection film. The optical multilayer film can be formed by a conventionally known method, such as a vapor deposition method or a sputtering method.

[0063] An adhesion-strengthening film may be provided between the glass and the optical multilayer film. This improves the adhesion between the glass and the optical multilayer film, and prevents the film from peeling off. Examples of the adhesion-strengthening film include silicon oxide (SiO ２ ), titanium oxide (TiO ２ ), lanthanum titanate (La ２ Ti ２ O ７ ), aluminum oxide (Al ２ O ３ ), aluminum oxide and zirconium oxide (ZrO ２ ), a mixture with magnesium fluoride (MgF ２ ), calcium fluoride (CaF ２ ), strontium fluoride (SrF ２), fluorine silicone, etc. Substances containing fluorine or oxygen have higher adhesion, and magnesium fluoride and titanium oxide are particularly preferred because they have high adhesion to glass and films. The adhesion-strengthening film may be a single layer or two or more layers. In the case of two or more layers, a combination of multiple substances may be used.

[0064] The near-infrared absorption cut filter according to this embodiment may include an absorption layer containing a near-infrared absorbing material having a maximum absorption wavelength in the near-infrared region, on at least one main surface of the glass of this embodiment. By adopting such a configuration, it is possible to obtain an optical filter having a lower transmittance of light in the near-infrared region.

[0065] The near-infrared absorption cut filter according to this embodiment is preferably made of a transparent resin selected from acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, and polyester resins, and is preferably made of one of these resins alone or a mixture of two or more thereof, and the near-infrared absorbing dye is added to the transparent resin and contained in the absorbing layer.Furthermore, it is preferable to use, as the near-infrared absorbing dye, a near-infrared absorbing material composed of at least one selected from the group consisting of squarylium dyes, phthalocyanine dyes, cyanine dyes, and diimmonium dyes.

[0066] <<Solid-state imaging device>> The solid-state imaging device according to this embodiment includes the near-infrared absorption cut filter described above in <<Near-infrared absorption cut filter>>. Preferred aspects of this near-infrared absorption cut filter are also the same as the preferred aspects described above in <<Near-infrared absorption cut filter>>.

[0067] The solid-state imaging device according to this embodiment includes an imaging lens in addition to the near-infrared absorption cut filter.

[0068] The solid-state imaging device converts input light into an electrical signal and outputs the signal to an image signal processing circuit. Examples of the solid-state imaging device include a Charge Coupled Device (CCD) image sensor and a Complementary Metal Oxide Semiconductor (CMOS) image sensor.

[0069] The imaging device using the solid-state imaging element further includes an imaging lens. The near-infrared absorption cut filter may be disposed between the imaging lens and the solid-state imaging element. The near-infrared absorption cut filter may be provided independently of the solid-state imaging element, and may be directly attached to the imaging lens or the like via an adhesive layer, for example.

[0070] <<Method for Producing Glass>> One embodiment of the method for producing the glass described above in <<Glass>> will be described below. However, the production method is not limited to the following embodiment.

[0071] The method for producing glass according to this embodiment includes the following steps: Step 1: weighing and mixing glass raw materials to obtain a raw material mixture; Step 2: heating and melting the raw material mixture obtained in Step 1; and Step 3: shaping the melt obtained in Step 2.

[0072] The glass obtained in step 3 above is {[H ＋ Ａ ] / [H ＋ Ｂ ]} is not 2 or less, it is preferable to further include a post-treatment step as step 4.

[0073] <Step 1> Step 1 may be carried out using a conventionally known method. For example, the content of P in the obtained glass expressed in mole percent based on oxides is ２ O ５ :30~50%, Al ２ O ３ : 1 to 10%, ΣR ２ O: 10-35%, ΣR'O: 0-10%, CuO: 1-15%, TiO ２ : 0-10%, WO ３ : 0 to 10%, and Nb ２ O５ : 0 to 10% of the raw material mixture can be obtained without going through step 4. ＋ Ａ ] / [H ＋ Ｂ ]} is preferably 2 or less, since it is easy to obtain a glass in which the ratio is 2 or less.

[0074] <Step 2> Conventionally known methods and conditions can be adopted for the heating and melting conditions in Step 2, but the heating temperature is preferably 700 to 1450°C. Here, from the viewpoint of suppressing the occurrence of devitrification and from the viewpoint of shortening the production time, the heating temperature is preferably 700°C or higher, more preferably 800°C or higher, even more preferably 900°C or higher, and even more preferably 1000°C or higher. Furthermore, from the viewpoint of suppressing a decrease in transmittance of light in the visible range, the heating temperature is preferably 1450°C or lower, more preferably 1400°C or lower, even more preferably 1350°C or lower, and even more preferably 1300°C or lower.

[0075] <Step 3> Step 3 is a step of shaping the melt obtained in step 2. If necessary, an oxidizing agent may be added or clarification may be carried out between steps 2 and 3. Examples of additives and clarification agents include nitrate compounds and sulfate compounds having glass-forming cations. The oxidizing agent is a compound that oxidizes 100% of the total amount of Cu in the glass. ２＋ Increasing the proportion of ions has the effect of improving the transmittance of light in the visible range and improving the absorption of light in the near-infrared range.

[0076] The amount of the nitrate compound or sulfate compound added is preferably 0.5 to 10 mass% based on the raw material mixture. From the viewpoint of further improving the transmittance of light in the visible range, the amount added is preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 3 mass% or more. Furthermore, from the viewpoint of the effect of the addition reaching a plateau and from the viewpoint of glass formability, the amount added is preferably 10 mass% or less, more preferably 8 mass% or less, and even more preferably 6 mass% or less.

[0077] Examples of nitrate compounds include Al(NO ３ ) ３ , LiNO ３ , NaNO ３ , KNO ３ , Ca(NO３ ) ２ , Sr(NO ３ ) ２ , Ba(NO ３ ) ２ , Zn(NO ３ ) ２ , Cu(NO ３ ) ２ Examples of sulfate compounds include Al ２ (SO ４ ) ３ ・16H ２ O, Li ２ SO ４ , Na ２ SO ４ , K. ２ SO ４ , CaSO ４ , SrSO ４ , BaSO ４ , ZnSO ４ , CuSO ４ etc.

[0078] <Step 4> Step 4 is optional, but it is a step of removing the {[H ＋ Ａ ] / [H ＋ Ｂ ]} does not satisfy the condition of 2 or less, it is preferable to further include a post-treatment step as step 4. The post-treatment method is ＋ Concentration [H ＋ Ａ ] is small, and examples of the treatment include surface polishing, heat treatment, chemical treatment, gas treatment, ion exchange treatment, plasma treatment, etc. Heat treatment is preferably carried out at a temperature near the glass transition temperature (Tg) of the glass, and more preferably at a temperature in the range of (Tg±100)°C. The chemical used in the chemical treatment can be an acidic, neutral, or alkaline solution selected as appropriate to the extent that the glass surface is not deteriorated.

[0079] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Examples 1 to 4 and 6 to 16 are working examples, and Example 5 is a comparative example.

[0080] Test Examples Example 1 Glass raw materials were weighed and mixed to obtain a raw material mixture with the composition shown in Table 1. The raw material mixture was then heated and melted at 1100°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold, and slowly cooled. Next, polishing was performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 450°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 450°C for 12 hours. Note that the "-" in "Composition (mol %)" in Table 1 means that it was not intentionally added as a glass raw material. The same applies to Tables 2 and 3.

[0081] Example 2 A glass was obtained in the same manner as in Example 1, except that the obtained glass was subjected to a post-treatment of heat treatment in a nitrogen atmosphere at 450° C. for 12 hours.

[0082] Example 3 A glass was obtained in the same manner as in Example 1, except that the obtained glass was not subjected to post-treatment.

[0083] Example 4: Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 1. The raw material mixture was then heated and melted at 1,050°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold, and slowly cooled. Polishing was then performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 460°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 450°C for 12 hours.

[0084] Example 5 A glass was obtained in the same manner as in Example 4, except that no post-treatment was carried out.

[0085] Example 6: Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 2. The raw material mixture was then heated and melted at 1250°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold and slowly cooled. Next, a glass having a size of 40 mm x 30 mm and a thickness of 0.21 mm was obtained by polishing. The glass transition temperature of this glass was not measured.

[0086] Example 7: Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 2. The raw material mixture was then heated and melted at 1200°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold, and slowly cooled. Polishing was then performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 433°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 425°C for 24 hours.

[0087] Example 8 A glass was obtained in the same manner as in Example 7, except that the obtained glass was subjected to a post-treatment of heat treatment in air at 440° C. for 48 hours.

[0088] Example 9: Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 2. The raw material mixture was then heated and melted at 1200°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold and slowly cooled. Polishing was then performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 438°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 425°C for 24 hours.

[0089] Example 10 A glass was obtained in the same manner as in Example 9, except that no post-treatment was carried out.

[0090] Example 11 Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 3. The raw material mixture was then heated and melted at 1200°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold, and slowly cooled. Polishing was then performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 433°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 405°C for 24 hours.

[0091] Example 12 A glass was obtained in the same manner as in Example 11, except that the obtained glass was subjected to a post-treatment of heat treatment in air at 420° C. for 48 hours.

[0092] Example 13 Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 3. The raw material mixture was then heated and melted at 1200°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold, and slowly cooled. Polishing was then performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 401°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 390°C for 24 hours.

[0093] Example 14 Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 3. The raw material mixture was then heated and melted at 1200°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold, and slowly cooled. Polishing was then performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 399°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 404°C for 48 hours.

[0094] Example 15 Glass raw materials were weighed and mixed to obtain a raw material mixture having the composition shown in Table 3. The raw material mixture was then heated and melted at 1300°C for 2 hours. The resulting melt was refined and stirred, then poured into a mold, and slowly cooled. Polishing was then performed to obtain a glass measuring 40 mm x 30 mm and 0.21 mm thick. The glass transition temperature of this glass was 408°C. Further, as a post-treatment, heat treatment was performed in an air atmosphere at 378°C for 48 hours.

[0095] Example 16 A glass was obtained in the same manner as in Example 15, except that no post-treatment was carried out.

[0096] 《Evaluation》 〈[H ＋ Ａ ] / [H ＋ Ｂ The obtained glass was analyzed for H up to a depth of 20 μm from the surface of the glass using a secondary ion mass spectrometer (ADEPT1010, manufactured by ULVAC-PHI, Inc.). ＋The concentration (cps) was measured under the following conditions: Measurement conditions [SIMS measurement conditions] Primary ion species: Cs+ Primary ion acceleration voltage: 5 kV Primary ion current value: 500 nA Primary ion incident angle: 60° with respect to the normal to the sample surface Primary ion raster size: 300 × 300 μm ２ Polarity of secondary ions: negative Secondary ion detection area: 60 x 60 μm ２ (4% of the primary ion raster size) ESA Input Lens: 0 Neutralization gun used: Yes Method for converting the horizontal axis from sputtering time to depth: The depth of the analyzed crater is measured using a stylus surface profiler (Dektak150, manufactured by Veeco) to determine the primary ion sputtering rate. This sputtering rate is used to convert the horizontal axis from sputtering time to depth. Field Axis Potential during 1H-detection: The optimal value may vary depending on the device. The operator should carefully set the value so that the background is sufficiently removed.

[0097] The curve obtained by the above measurement is approximated by a sigmoid curve to determine the H ＋ Concentration [H ＋ Ａ ] (cps) and H at a depth of 100 μm from the surface of the glass ＋ Concentration [H ＋ Ｂ The results are shown in Tables 1 to 3.

[0098] <β-OH Value> The obtained glass was measured using a Fourier transform infrared spectrometer (Nic-plan / Nicolet 6700, manufactured by Thermo Fisher Scientific) at 400 cm －１ ~4000cm －１ The transmittance was measured at 2 cm. －１ The number of accumulations was 16, and a TGS detector was used. －１ ~4000cm －１ The maximum transmittance at T ０ , 3550 cm －１ The transmittance at T １When the thickness of the glass is d (mm), the value expressed by the following formula was taken as the β-OH value: β-OH value = -(1 / d) (log １０ (T １ / T ０ The β-OH values ​​obtained are shown in Tables 1 to 3.

[0099] <Transmittance> The internal transmittance of the obtained glass in the wavelength range of 400 to 1200 nm was measured using a spectrophotometer (V-570, manufactured by JASCO Corporation). ｉ２ =T ｉ１ ｔ２／ｔ１ The transmittance was converted into the transmittance when the glass thickness was 0.2 mm based on the following formula: Tables 1 to 3 show the transmittance results at wavelengths of 550 nm, 800 nm, and 1200 nm.

[0100] <Weather Resistance> The obtained glass was left for 100 hours in an environment of 85°C and 85% RH, and then the weather resistance was evaluated by visually inspecting for any changes in appearance. Specifically, a glass with minimal deterioration on the surface after the test was evaluated as "Good," and a glass with significant deterioration due to elution of glass components onto the surface and dripping was evaluated as "Poor." A rating of "Good" was used to determine good weather resistance. The diffuse transmittance and total luminous transmittance were then measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH5000). The value expressed as [diffuse transmittance / total luminous transmittance] was calculated as haze (%). A haze value of 15% or less was considered to indicate good weather resistance, with smaller values ​​being more preferable. The weather resistance evaluation results obtained are shown in Tables 1 to 3. In Tables 2 and 3, values ​​for which the haze value was not measured are indicated as "no data."

[0101]

[0102]

[0103]

[0104] From the above results, it can be seen that in glass containing phosphorus and a near-infrared absorbing component, {[H ＋ Ａ ] / [H ＋ Ｂ]} is 2 or less, the deterioration of the glass under high temperature and high humidity conditions is small, the haze value is small, and the weather resistance is improved. ＋ Ａ ] / [H ＋ Ｂ ]} exceeds 2, weather resistance can be improved by performing post-treatment to reduce the ratio to 2 or less. ＋ Ａ ] / [H ＋ Ｂ When post-treatment is performed on glass having a composition in which the ratio represented by {\displaystyle \mathrm {R} / \mathrm {R}} is 2 or less, the ratio becomes even smaller, and not only the weather resistance but also the transmittance of light in the visible range tends to improve.

[0105] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-119934) filed on July 24, 2023, the contents of which are incorporated herein by reference.

Claims

1. In mole percent based on oxide, P ２ O ５ and a total of 0.5% or more of near infrared absorbing components, ＋ Concentration [H ＋ Ａ ] and H at a depth of 100 μm from the surface of the glass ＋ Concentration [H ＋ Ｂ ] with {[H ＋ Ａ ] / [H ＋ Ｂ ]} is 2 or less.

2. β-OH value is 1mm －１ 2. The glass of claim 1 , wherein:

3. The {[H ＋ Ａ ] / [H ＋ Ｂ 2. The glass of claim 1 , wherein the ratio represented by {R(t) / R(t)} is less than 1.

4. The glass according to claim 1, which has a transmittance of 70% or more at a wavelength of 550 nm when converted into a glass with a thickness of 0.2 mm.

5. The glass according to claim 1, which has a transmittance of 30% or less at a wavelength of 800 nm when converted into a glass with a thickness of 0.2 mm.

6. The glass according to claim 1, which contains at least one element selected from the group consisting of Cu, Fe, and V as the near infrared absorbing component.

7. The glass according to claim 1, containing Cu as the near infrared absorbing component, and containing 0.5% or more of CuO, expressed in mole percent on an oxide basis.

8. The glass according to claim 1, which contains at least one element selected from the group consisting of Ti, W and Nb.

9. In terms of mole percent based on oxide, TiO ２ , W.O. ３ and Nb ２ O ５ The glass according to claim 8, comprising a total of 5% or more.

10. The content in mole percent on an oxide basis is P ２ O ５ :25~80%, Al ２ O ３ : 1-20%, ΣR ２ O: 0 to 35% (wherein R represents Li, Na, K, Rb, and Cs), ΣR′O: 0 to 30% (wherein R′ represents Mg, Ca, Sr, Ba, and Zn), and CuO: 0.5 to 30%, ２ O is Li ２ O, Na ２ O.K. ２ O, Cs ２ O and Rb ２ 2. The glass according to claim 1, wherein ΣR′O means the total content of MgO, CaO, SrO, BaO, and ZnO.

11. The content in mole percent on an oxide basis is P ２ O ５ :30~50%, Al ２ O ３ : 1-10%, ΣR ２ O: 10 to 35% (wherein R represents Li, Na, K, Rb, and Cs), ΣR′O: 0 to 10% (wherein R′ represents Mg, Ca, Sr, Ba, and Zn), CuO: 1 to 15%, TiO ２ : 0-10%, WO ３ : 0 to 10%, and Nb ２ O ５ : 0 to 10%, ２ O is Li ２ O, Na ２ O.K. ２ O, Cs ２ O and Rb ２ 2. The glass according to claim 1, wherein ΣR′O means the total content of MgO, CaO, SrO, BaO, and ZnO.

12. The glass according to claim 1, wherein the F content, expressed in mole percent, is 7% or less.

13. A near-infrared absorption cut filter comprising the glass according to any one of claims 1 to 12.

14. A solid-state imaging device comprising the near-infrared absorption cut filter according to claim 13.

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