WO2013152628A1

WO2013152628A1 - Near infrared light absorption glass, element and light filter

Info

Publication number: WO2013152628A1
Application number: PCT/CN2013/070069
Authority: WO
Inventors: 孙伟; 李小春; 匡波
Original assignee: 成都光明光电股份有限公司
Priority date: 2012-04-11
Filing date: 2013-01-05
Publication date: 2013-10-17
Also published as: CN102923948A; JP6047226B2; KR20150007302A; CN107140829A; JP2015522499A; KR101630562B1

Abstract

An environment-friendly near infrared light absorption glass with thin glass, superior chemical stability and visible light transmittance, and a near infrared light absorption element and a light filter formed by the glass. When the thickness of the near infrared light absorption glass is 0.3 mm, the transmittance at a wavelength of 400 nm is greater than 83%, and the transmittance at a wavelength of 500 nm is greater than 85%. The near infrared light absorption glass contains P⁵⁺, Al³⁺, R⁺, Τ²⁺, Ζn²⁺ and Cu²⁺ that are represented by positive ions. The R⁺ represents total amount of Li⁺, Na⁺ and K⁺. The Τ²⁺ represents total amount of Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺. The content of Cu²⁺ is 0.1%-4% of the weight of positive ions, and the content of Zn²⁺ is 1%-15% of the weight of positive ions. O^2— and F^- represented by negative ions are contained.

Description

Near-infrared light absorbing glass, components and filters

Technical field

The present invention relates to a near-infrared light absorbing glass, a near-infrared light absorbing element, and a near-infrared light absorbing filter. Specifically, the present invention relates to a near-infrared light absorbing glass excellent in chemical stability for a near-infrared light absorbing filter suitable for color sensitivity correction, and a near-infrared light absorbing element and a filter composed of the glass.

Background technique

In recent years, the spectral sensitivity of semiconductor imaging elements such as CCDs and CMOSs used in digital cameras and VTR cameras has spread to the near-infrared field around l lOOnm from the field of view, and can be approximated by using filters that absorb light in the near-infrared field. The degree of human vision. Therefore, the demand for color sensitivity correction filters is increasing, which places higher demands on the near-infrared light absorbing functional glass used for manufacturing such filters, that is, it is required to be supplied in large quantities at low prices. Such glass, and glass has better stability.

In the prior art, the near-infrared absorbing glass is a near-infrared light absorbing glass by adding CiT to phosphate glass or fluorophosphate glass. However, compared with fluorophosphate glass, phosphate glass has poor chemical stability. If the glass is exposed to high temperature and high humidity for a long time, cracks and white turbidity may occur on the surface of the glass. Further prior art solution is to eliminate the glass Cu ²⁺ is reduced to Cu ^+, to solve the technical problems transmittance near a wavelength of 400nm reduced glass by introduction of Sb ^3+, Sb ₂ 0 ₃ but introducing a certain impact on the environment .

In addition, the miniaturization and weight reduction of photovoltaic terminal products have promoted the thinning of near-infrared light absorbing filter glass. However, if the glass is directly thinned, the near-infrared light absorption is also small, and the desired spectral characteristics cannot be obtained. Therefore, the content of the coloring component CiT is often increased to compensate for the decrease in absorption due to thinning, and the near-infrared absorption filter is used. When the concentration of CiT in the light glass is high, the valence of CiT changes, and the transmittance near 400 nm decreases to become blue-green. In addition, if the amount of CiT is increased, the devitrification resistance of the glass is deteriorated, and crystals in the glass are easily precipitated.

Summary of the invention

The technical problem to be solved by the present invention is to provide an environmentally friendly, thin glass having a thin A near-infrared light absorbing glass having excellent chemical stability, excellent transmission characteristics in a visible region, and a near-infrared light absorbing member and a filter composed of the glass.

The technical solution adopted by the present invention to solve the above technical problem is: near-infrared light absorbing glass, the near-infrared light absorbing glass has a thickness of 0.3 mm, and the transmittance at a wavelength of 400 nm shows greater than 83%, and the transmittance at a wavelength of 500 nm. Showing greater than 85%, the near-infrared light absorbing glass contains P ⁵⁺ , Al ³⁺ , R Ί ² Zn ²⁺ and Cu ²⁺ represented by cations, and the R ⁺ represents Li ⁺ , Na ⁺ and K ⁺ Total, the T ²⁺ represents the total amount of Mg ²⁺ , Ca ²⁺ , S and Ba ²⁺ , the CiT content is 0. 1-4%, the content of Zn ²⁺ is 1-15%, and is used at the same time. The anion represents 0 ² — and F―.

Further, when the near-infrared light absorbing glass has a thickness of 0.3 mm, the transmittance at a wavelength of 400 nm is more than 88%, and the transmittance at a wavelength of 500 nm is more than 90%.

Further, containing 15-40% of P ⁵⁺ ; 5-20% of Al ³⁺ ; R ⁺ content of 1-35%; T ²⁺ content of 30-55%; 0. 1-4% The total amount of Cu ²⁺ ; 1-15% Zn ²⁺ ; 0 ² - and F- is 96% or more.

Further, containing 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; R + content of 3-30%; T ²⁺ content of 40-50%; 0. 5-3. % Cu ²⁺ ; more than 6% but less than 12% of Zn ²⁺ ; 0 ² - and F - total amount is 97% or more.

Further, it contains 25-30% P ⁵⁺ ; 10-15% Al ³⁺ ; R ⁺ content is 5-15%; T ²⁺ content is 42-48%; 1-3. 9% The total amount of Cu ²⁺ ; 6. 5- 10% Zn ²⁺ ; 0 ² - and F- is 99% or more.

Further, containing 15-40% of P ⁵⁺ ; 5- 20% of Al ³⁺ ; 1-15% of Li ⁺ ; 0 -15% of Na+; 0-5% of K+; 0. 1-10 % Mg ²⁺ ; 1-20% Ca ²⁺ ; 0-15% Sr ²⁺ ; greater than 30% but less than 45% Ba ²⁺ ; 0. 1-4% Cu ²⁺ ; 001-1% The total amount of Zn ²⁺ ; 0 ² - and F - is 96% or more; the total amount of CI -, Br - and I is 0. 001-1%

Further, containing 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-10% of Li+; 1-12% of Na+; 0-5% of K ⁺ ; 2-8% Mg ²⁺ ; 3- 15% Ca ²⁺ ; 0-10% Sr ²⁺ ; 31-42% Ba ²⁺ ; 0. 5-3. 9% Cu ²⁺ ; more than 6% but less than 12 005-0. 5%。 The total amount of Zn ²⁺ ; 0 ² - and F - is more than 97%; the total amount of CI -, Br - and I is 0. 005-0. 5%.

Further, containing 25-30% P ⁵⁺ ; 10-15% Al ³⁺ ; 2-6% Li+; 2- 10% Na+; 0-5% K+; 3-7% Mg ²⁺ _; 5-1 1% Ca ²⁺ ; 0-5% Sr ²⁺ ; 31- 40% Ba ²⁺ ; 1-3. 9% Cu ²⁺ ; 6. 5-10% Zn ²⁺ ; 0 ² — and F—the total amount is 99% or more; CI—, Br— and I— 1重量。 The measurement is 0.009-0. 1%.

Near-infrared light absorbing glass containing 15-40% P ⁵⁺ ; 5-20% A1 ³⁺ ; R ⁺ content is 1-35%; T ²⁺ content is 30-55%; 0. 1- The total amount of 4% Cu ²⁺ ; 1-15% Zn ²⁺ ; 0 ² - and F- is 96% or more, and the R+ represents the total amount of Li+, Na ⁺ and K ⁺ , the Τ ^{2 +} represents the total amount of Mg ²⁺ , Ca ²⁺ , S and Ba ²⁺ .

Further, it contains 20-35% P ⁵⁺ ; 10-15% Al ³⁺ ; R ⁺ content is 3-30%; T ²⁺ content is 40-50%; 0.5-3.9% Cu ²⁺ ; more than 6% but less than 12% of Zn ²⁺ ; 0 ² - and the total amount of F - is 97% or more.

Further, it contains 25-30% P ⁵⁺ ; 10-15% Al ³⁺ ; R+ content is 5-15%; T ²⁺ content is 42-48%; 1-3.9% Cu ^{2 +} ; 6.5-10% of Zn ²⁺ ; 0 ² - and the total amount of F - is more than 99%.

Further, containing 15-40% of P ⁵⁺ ; 5- 20% of Al ³⁺ ; 1-15% of Li ⁺ ; 0 -15%

Na+; 0-5% K+; 0. 1-10% Mg ²⁺ ; 1-20% Ca ²⁺ ; 0-15% Sr ²⁺ ; more than 30% but less than 45% Ba ²⁺ _; 0. 1-4% Cu ²⁺ ; 1-15% Zn ²⁺ ; 0 ² - and F - total amount is 96% or more;

The total amount of CI—, Br— and I is 0.001-1%

Further, containing 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-10% of Li ⁺ ; 1-12%

Na+; 0-5% K ⁺ ; 2-8% Mg ²⁺ ; 3- 15% Ca ²⁺ ; 0-10% Sr ²⁺ ; 31-42% Ba ²⁺ ;

0.5-3.9% Cu ²⁺ ; more than 6% but less than 12% Zn ²⁺ ; the total amount of 0 ² - and F- is 97% or more;

The total amount of CI—, Br— and I is 0.005-0.5%.

Further, containing 25-30% P ⁵⁺ ; 10-15% Al ³⁺ ; 2-6% Li+; 2- 10% Na+; 0-5% K ⁺ ; 3-7% Mg ²⁺ ; 5- 11% Ca ²⁺ ; 0-5% Sr ²⁺ ; 31-40% 8 &²⁺; 1-3.9% Cu ²⁺ ; 6.5-10% Zn ²⁺ ; 1%。 The total amount of ² - and F - is more than 99%; CI -, Br - and I - the total amount is 0.009-0. 1%.

Na+; 0-5% K+; 0. 1-10% Mg ²⁺ ; 1-20% Ca ²⁺ ; 0-15% Sr ²⁺ ; more than 30% but less than 45% Ba ²⁺ ; 0. 1-4% Cu ²⁺ ; 1-15% Zn ²⁺ ; the total amount of Ba ²⁺ and Na ⁺ is greater than

30% but less than 60%; 50-70% of 0 ² -; 30- 50% of F-; CI-, Br- and I are

0.001-1%.

Further, containing 20-35% P ⁵⁺ ; 10-15% Al ³⁺ ; 2-10% Li+; 1-12% Na+; 0-5% K ⁺ ; 2-8% Mg ²⁺ ; 3- 15% Ca ²⁺ ; 0-10% Sr ²⁺ ; 31-42% Ba ²⁺ ; 3. 9% Cu ²⁺ ; more than 6% but less than 12% Zn ²⁺ ; the total amount of Ba ²⁺ and Na ⁺ is 32-50%; 55-65% 0 ² —; 35-45% 005-0. 5% The total amount of the C-, Br-, and I- is 0. 005-0. 5%

Further, containing 25-30% P ⁵⁺ ; 10-15% Al ³⁺ ; 2-6% Li+; 2- 10% Na+; 0-5% K+; 3-7% Mg ²⁺ _; 5-1 1% Ca ²⁺ ; 0-5% Sr ²⁺ ; 31- 40% Ba ²⁺ ; 1-3. 9% Cu ²⁺ ; 6. 5-10% Zn ²⁺ ; The total amount of Ba ²⁺ and Na ⁺ is 33-46%; 57-63% of 0 ² —; 37-43% of F—; CI—, Br— and I—the total amount is 0. 009 -0. 1%

Further, containing 25-30% P ⁵⁺ ; 10-15% Al ³⁺ ; 2-6% Li+; 2- 10% Na+; 0-5% K+; 3-7% Mg ²⁺ _; 5-1 1% Ca ²⁺ ; 0-5% Sr ²⁺ ; 31- 40% Ba ²⁺ ; 1-3. 9% Cu ²⁺ ; 6. 5- 10% Zn ²⁺ ; 57- 63% of 0 ² —; 37-43% of F—; 0. 01-0. 07% of C1 is further entangled, at a wavelength of 400-700 nm, the transmittance of the glass 5毫米之间。 The thickness of 0. 2-0. 5mm between.

The near-infrared light absorbing element is composed of the above-described near-infrared light absorbing glass.

The near-infrared light absorbing filter is composed of the above-described near-infrared light absorbing glass.

The invention has the beneficial effects that: the invention adopts a specific glass composition design, uses fluorophosphate glass as the matrix glass, adds an appropriate amount of Cu ²⁺ , introduces Zn ²⁺ , Na ^{+ to} make the glass chemical stability excellent, and the glass water resistance stability D _w (powder method) reaches grade 1, acid resistance stability (powder method) reaches or better than grade 4; at the same time, it is preferred not to introduce Sr ²⁺ in the glass composition, and increase Ba ²⁺ content to increase glass alkalinity, which is beneficial to The present invention can achieve the object of the invention. The glass has a thickness of 0.3 mm, the transmittance at a wavelength of 400 nm is greater than 83%, and the transmittance at a wavelength of 500 nm is greater than 85%. In the spectral transmittance in the wavelength range of 500 to 700 nm, the corresponding wavelength (i.e., λ ₅ .corresponding wavelength value) in the range of 50% is in the range of 635 to 655 nm.

DRAWINGS

Fig. 1 is a graph showing the spectral transmittance of a near-infrared light absorbing glass of Example 1 of the present invention. detailed description

The near-infrared light absorbing glass of the present invention is obtained by adding a fluorophosphoric acid glass as a base and adding a CiT having a near-infrared light absorbing effect.

In the following, the cationic component content is 100% of the total weight of the total cation by the weight of the cation. P ⁵⁺ is an essential component of fluorophosphate glass and is an important component for generating absorption in the infrared region of CiT. When the content is less than 15%, the color correction function deteriorates and is green; when it exceeds 40%, the weather resistance and the devitrification resistance deteriorate, so the content of P ⁵⁺ is limited to 15-40%, preferably 20-35%. More preferably, it is 25-30%.

Al ³⁺ is a component that improves the devitrification resistance, weather resistance, thermal shock resistance, mechanical strength and chemical resistance of fluorophosphate glass. When the Al ³⁺ content is less than 5%, the above effects are not obtained; when the Al ³⁺ content exceeds 20%, the near-infrared absorption characteristics are lowered. Therefore, the Al ³⁺ content is 5-20%, more preferably 10-15%.

R ⁺ is a component that increases the meltability, glass-forming, and transmittance of the visible light region of the glass. Here, R ⁺ represents the total amount of Li ⁺ , Na ⁺ and K ⁺ , and if the content of R ⁺ exceeds 35%, the chemical durability of the glass is remarkably lowered. Therefore, the R ⁺ total content ranges from 1 to 35%, preferably from 3 to 30%, more preferably from 5 to 15%.

Compared with Na ⁺ and K ⁺ , the introduction of Li ^{+ has} a better effect on the chemical stability of the glass. However, when the Li ⁺ content exceeds 20%, the durability and processability of the glass deteriorate. Therefore, the Li ⁺ content is 1-15%, preferably 2-10%, more preferably 2-6%.

In the present invention, it is also preferable to add a small amount of Na ⁺ and Li ^{+ to} be melted, which can effectively improve the weather resistance of the glass, and at the same time, can significantly increase the alkalinity of the glass liquid, and the glass has excellent near-infrared light absorption performance. The Na ⁺ content is 0-15%, preferably 1-12%, more preferably 2-10%. The K ⁺ content is 0-5%, and if the content exceeds 5%, the durability of the glass is rather lowered.

Τ ²⁺ is a component that effectively improves the glass-forming, devitrification resistance, and processability of glass, where Τ ²⁺ represents Mg ²⁺ , Ca ²⁺ , Sr ^{2+ ,} and Ba ²⁺ . As a near-infrared light absorbing filter, it is desirable that the light transmittance of the visible region is high. In order to increase the transmittance of the visible field, the introduced copper ions are not Cu ⁺ and must be Cu ²⁺ . When the glass solution is in a reduced state, CiT becomes Cu ⁺ , and as a result, the transmittance near a wavelength of 400 nm is lowered. When the total content of T ²⁺ in the present invention is less than 30%, the devitrification resistance tends to be deteriorated, and if it exceeds 55%, the devitrification resistance tends to be deteriorated. Therefore, the total content of Τ ²⁺ is from 30 to 55%, preferably from 40 to 50% by total, more preferably from 4 to 24%.

Among them, Mg ²⁺ and Ca ²⁺ have an effect of improving the resistance to devitrification, chemical stability, and processability of the glass. The Mg ²⁺ content is preferably from 0.1 to 10%, more preferably from 2 to 8%, further preferably from 3 to 7%. The Ca ²⁺ content is preferably from 1 to 20%, more preferably from 3 to 15%, further more preferably from 5 to 1 1%.

Ba ²⁺ and Sr ²⁺ have an effect of improving glassiness, glass resistance to devitrification, and melting. Wherein the Ba ²⁺ content is preferably greater than 30% but less than 45%, more preferably from 31 to 42%, and most preferably from 3 to 40%. The Sr ²⁺ content is preferably from 0 to 15%, more preferably from 0 to 10%, most preferably from 0 to 5%.

In addition, the present invention mainly introduces a high content of Ba ²⁺ into the glass composition, preferably does not introduce Sr ²⁺ , and achieves the purpose of effectively improving the chemical stability of the glass, and by adjusting the total amount of Ba ²⁺ and Na ⁺ , It can effectively increase the alkalinity of glass to improve its near-infrared light absorption performance. The total amount of Ba ²⁺ and Na ⁺ is preferably more than 30% but less than 60%, further preferably 32-50%, more preferably 33-46%.

The invention can effectively increase the alkalinity of the glass liquid by introducing Zn ²⁺ , and the alkaline environment of the glass liquid is favorable for the copper ions to exist in the form of CiT, so that more Cu ²⁺ can be introduced into the matrix glass to increase the glass. Near-infrared light absorption performance; in addition, in the composition of the invention, Zn ²⁺ and P ⁵⁺ can make the glass have excellent chemical stability, especially the glass has excellent water resistance; therefore, the content of Zn ²⁺ is

1- 15%, preferably in the range of more than 6% but less than 12%, more preferably in the range of 6.5 to 10%.

The copper ions in the glass are the main indicators of the near-infrared absorption characteristics and are present as CiT. 1-4%,优选为0. 5。 1-4%, preferably 0. 5 1-4%, preferably 0. 5 1-4%, preferably 0. 5 9%。 More preferably 1-3. 9%.

The glass of the present invention contains 0 ² - and F - as an anion component. 0 ² — is an important anion component in the glass of the present invention. When the content of 0 ² - is too small, since CiT is reduced to Cu ⁺ , absorption in a short wavelength region, particularly near 400 nm, becomes more Large until the display is green; but when

When the content of 0 ² - is too large, since the viscosity of the glass becomes higher to cause a higher melting temperature, the transmittance is lowered. Therefore, the content of 0 ² - in the present invention is 50-70%, preferably 55-65%, more preferably 57-63%.

In the near-infrared absorbing glass, when the melting temperature is raised, CiT is easily reduced to Cu ⁺ , and the color of the glass changes from blue to green, thereby impairing the characteristics necessary for applying color sensitivity correction to the semiconductor imaging element. The present invention preferably has an appropriate amount of F-content to make the glass excellent in chemical stability. Therefore, the preferred range of F- is 30-50%, and further preferably 35-45%, the most preferred range It is 37-43%.

Further, in order to remove bubbles generated during the melting of the glass, it is preferable to select one or more clarifiers to be selected from the group consisting of 0 ² - and F -, Cl -, Br - and I - as an anion component. If the total content of Cl—, Br— and I— is less than 0.001%, it is difficult to sufficiently obtain the bubbles generated during the melting of the glass. If the total content exceeds 1%, CiT is reduced to Cu ⁺ . The transmittance near the wavelength of 400 nm deteriorates. 009-0. 1%, More preferably, the content is 0. 009-0%, more preferably 0. 009-0. 1%, more preferably 0. 009-0. The most preferred content is 0. 01-0. 07%

Among Cl-, Br- and I-, the best effect is Cl-, therefore, in Cl-, Br- and Γ, it is desirable to add only Cl-. 01%. The most preferred content is 0. 00-0. 07%. The most preferred content is 0. 01-0. 07%.

The near-infrared light absorbing glass of the present invention is a fluorophosphate glass, and most of the anion components are 0 ² - and F-. Gp, as the total content of 0 ² - and F -, 95% or more can be targeted. In order to achieve superior weather resistance, high transmittance in the vicinity of a wavelength of 400 nm, and excellent devitrification resistance, the total content of 0 ² - and F- is 96% or more, and more preferably The content is 97% or more, and the optimum is 99% or more.

The characteristics of the glass of the present invention will be described below.

The transmittance of the glass varies depending on the thickness. If the thickness and transmittance of the glass in the light transmission direction are known, the transmittance of a predetermined thickness can be obtained by calculation.

When the thickness of the glass of the present invention is 0.3 mm, the spectral transmittance in the wavelength range of 400 to 1200 nm has the characteristics shown below.

The spectral transmittance at a wavelength of 400 nm is greater than or equal to 83%, preferably greater than or equal to 85%, more preferably greater than or equal to 88%.

The spectral transmittance at a wavelength of 500 nm is greater than or equal to 85%, preferably greater than or equal to 88%, more preferably greater than or equal to 90%.

The spectral transmittance at a wavelength of 600 nm is greater than or equal to 60%, preferably greater than or equal to 65%, more preferably greater than or equal to 70%.

The spectral transmittance at a wavelength of 700 nm is less than or equal to 30%, preferably less than or equal to 26%, more preferably less than or equal to 24%. The spectral transmittance at a wavelength of 800 nm is less than or equal to 15%, preferably less than or equal to 10%, more preferably less than or equal to 9%.

The spectral transmittance at a wavelength of 900 nm is less than or equal to 15%, preferably less than or equal to 13%, more preferably less than or equal to 11%.

The spectral transmittance at a wavelength of lOOOnm is less than or equal to 25%, preferably less than or equal to 20%, more preferably less than or equal to 18%.

The spectral transmittance at a wavelength of l lOOnm is less than or equal to 35%, preferably less than or equal to 32%, more preferably less than or equal to 29%.

The spectral transmittance at a wavelength of 1200 nm is less than or equal to 50%, preferably less than or equal to 45%, more preferably less than or equal to 41%.

That is, when the thickness of the glass of the present invention is 0.3 mm, the absorption in the wavelength range of the near-infrared region of 700 nm to 1200 nm is large, and the absorption in the wavelength range of the visible light region of 400 nm to 600 nm is small. In the spectral transmittance in the wavelength range of 500 nm to 700 nm, the corresponding wavelength (i.e., λ ₅ .corresponding wavelength value) when the transmittance is 50% ranges from 631 to 655 nm, preferably ranges from 635 to 650 nm, and more preferably 640. - 646nm.

The singularity of the singularity of the singularity of the singularity of the singularity of the present invention. 5毫米之间。 Between, 0. 2-0. 5mm between. It is preferable that the transmittance at a wavelength of 400 nm at the thickness is 83% or more.

The transmittance of the glass of the present invention having a thickness of 0.3 mm is a transmittance of a glass having a wavelength of 400 to 1200 nm as measured by a spectrophotometer. Transmittance measured values in the manner described: Assuming that the glass sample has two planes that are parallel to each other and optically polished, light is incident perpendicularly from one parallel plane, exiting from another parallel plane, and the intensity of the exiting light is divided by the incident The intensity of light is the transmittance, which is also called the external transmittance.

According to the above characteristics of the glass of the present invention, color correction of a semiconductor imaging element such as CCD or CMOS can be excellently achieved.

The chemical stability characteristics of the glass are as follows: water resistance stability 0 „ can reach level 1; acid resistance stability reaches level 4, preferably up to level 3, more preferably up to level 2.

The above water resistance stability D _w (powder method) is calculated according to the test method of GB/T17129 according to the following formula: D _ff = ( BC) I ( BA) *100

Where: D _w — percentage of glass leaching (%)

B Filter and sample quality (g)

C Filter and quality of the sample after erosion (g)

A—filter quality (g)

From the calculated percentage of leaching, the water resistance stability of the optical glass D _{w is} divided into 6 categories as shown in the following table.

The above acid resistance stability D _A (powder method) According to the test method of GB/T17129, it is calculated according to the following formula:

D _A = ( BC) I ( BA) *100

Where: D _A - percentage of glass leaching (%)

B Filter and sample quality (g)

C Filter and quality of the sample after erosion (g)

A—filter quality (g)

From the calculated percentage of leaching, the acid resistance of the optical glass is stabilized. D _{A is} classified into 6 categories as shown in the following table.

The near-infrared light absorbing element according to the present invention is composed of the near-infrared light absorbing glass, and may be a thin plate-shaped glass element or a lens used in a near-infrared light absorbing filter, and is suitable for a solid-state image sensor. For color correction, it has good permeability and chemical stability. 0之间之间之间之间之间之间之间之间。 The thickness of the near-infrared light absorbing element (the distance between the incident surface and the exit surface of the transmitted light) is determined by the transmittance characteristics of the element, preferably between about 0. 1-0. 8mm, more preferably at 0. Between 2 and 2. 6 mm, most preferably between 0. 2-0. 5 mm, and preferably λ ₅ . Between 631 and 655 nm, particularly preferably 644 nm. In order to obtain such a near-infrared light absorbing element, the composition of the near-infrared light absorbing glass is adjusted to be processed into an element having the above-described spectral characteristic thickness.

The near-infrared filter according to the present invention is a near-infrared composed of near-infrared light absorbing glass. The light absorbing element is composed of a near-infrared light absorbing element composed of near-infrared light absorbing glass optically polished on both sides, and the color correction function of the filter is provided by the element, and the chemical stability is also achieved.

Example

Hereinafter, the present invention will be described in more detail with reference to the embodiments. However, the invention is not limited to the embodiment.

First, fluoride, metaphosphate, oxide, nitrate and carbonate are used as glass raw materials, and the raw materials are weighed to have the composition having the composition shown in Table 1, and after thorough mixing, the mixed raw materials are put into The platinum crucible sealed by a lid is heated and melted at a temperature of 700-90 CTC, and after clarification is simultaneously neutralized by oxygen gas, the molten glass is continuously discharged from the temperature control pipe at a constant flow rate, and the optical glass of the present invention is obtained after molding.

Table 1

The above glass is processed into a plate shape, and both sides opposed to each other are optically polished to prepare For the sample for measuring the transmittance, the spectral transmittance of each sample was measured using a spectrometer to obtain a transmittance of a typical wavelength of each sample having a thickness of 0.3 mm.

The transmittance values of the glass of the present invention at a thickness of 0.3 mm were shown in Table 2, and it was confirmed that the glass had excellent properties as a color sensitivity correction glass for a semiconductor imaging element.

Table 2

Figure 1 is a graph showing the spectral transmittance of the glass of Example 1 having a thickness of 0.3 mm. As can be seen from the figure, in the case where the glass thickness is 0.3 mm, the transmittance at a wavelength of 400 nm is preferably 83% or more. In the spectral transmittance in the wavelength range of 500 to 700 nm, the corresponding wavelength (i.e., λ ₅ . corresponding wavelength value) in the range of 50% transmittance is 631 to 655 nm. Among the spectral transmittances at a wavelength of 400 to 1200 nm, the transmittance in the wavelength region of the wavelength of 800 to 1000 nm is the lowest. Since this region is a near-infrared region, the sensitivity of the semiconductor image sensor in this region is not so low, and therefore it is necessary to suppress the transmittance of the color correction filter to a sufficiently low level. On the other hand, when the wavelength is in the region of 1000 to 1200 nm, the sensitivity of the semiconductor imaging element is relatively lowered, so that the transmittance of the glass of the present invention is increased.

Claims

Claim

The near-infrared light absorbing glass is characterized in that, when the thickness of the near-infrared light absorbing glass is 0.3 mm, the transmittance at a wavelength of 400 nm is greater than 83%, and the transmittance at a wavelength of 500 nm is greater than 85%. The near-infrared light absorbing glass contains P ⁵⁺ , Al ³⁺ , R ⁺ , T ²⁺ , Zn ²⁺ and Cu ²⁺ represented by a cation, and the R+ represents a total amount of Li+, Na ⁺ and K ⁺ , Τ ²⁺ represents the total amount of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ , CiT content is 0. 1-4%, Zn ²⁺ content is 1-15%, and contains an anion 0 ² — and F―.

2. The near-infrared light absorbing glass according to claim 1, wherein the near-infrared light absorbing glass has a thickness of 0.3 mm, and the transmittance at a wavelength of 400 nm is greater than 88%, and the transmittance at a wavelength of 500 nm. The display is greater than 90%.

The near-infrared light absorbing glass according to claim 1 or 2, characterized in that

15-40% P ⁵⁺ ; 5-20% Al ³⁺ ; R ⁺ content is 1-35%; T ²⁺ content is 30-55%; 0. 1-4% Cu ²⁺ ; The total amount of 1-15% Zn ²⁺ ; 0 ² - and F- is 96% or more.

The near-infrared light absorbing glass according to claim 1 or 2, which comprises 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; R ⁺ is 3-30%; The content of T ²⁺ is 40-50%; 0. 5-3. 9% Cu ²⁺ ; more than 6% but less than 12% Zn ²⁺ ; the total amount of 0 ² - and F- is 97% or more.

The near-infrared light absorbing glass according to claim 1 or 2, which comprises 25-30% of P ⁵⁺ ; 10-15% of Al ³⁺ ; R+ content of 5-15%; The content of ²⁺ is 42-48%; 1-3. 9% of Cu ²⁺ ; 6. 5-10% of Zn ²⁺ ; the total amount of 0 ² - and F- is 99% or more.

The near-infrared light absorbing glass according to claim 1 or 2, which contains 15-40% of P ⁵⁺ ; 5-20% of Al ³⁺ ; 1-15% of Li+; 0 -15 % Na+; 0-5% K+; 0. 1-10% Mg ²⁺ _; 1-20% Ca ²⁺ ; 0-15% Sr ²⁺ ; more than 30% but less than 45% Ba ^{2 +;} 0. 1-4% of Cu ^2+; 1-15% of Zn ^2+; 0 ² - the total amount of F- Wo port is at least 96%; total amount of CI-, Br-, and for 0.001 -1%.

The near-infrared light absorbing glass according to claim 1 or 2, which comprises 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-10% of Li+; % Na+; 0-5% K+; 2-8% Mg ²⁺ _; 3-15% Ca ²⁺ ; 0-10% Sr ²⁺ ; 31-42% Ba ²⁺ ; - 3.9% Cu ²⁺ ; more than 6% but less than 12% Zn ²⁺ ; 0 ² - and F - total amount is 97% or more; CI -, Br - and I - 005-0. 5

The near-infrared light absorbing glass according to claim 1 or 2, which comprises 25-30% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-6% of Li ⁺ ; 2- 10% Na ⁺ ; 0-5% K ⁺ ; 3-7% Mg ²⁺ ; 5- 11% Ca ²⁺ ; 0-5% Sr ²⁺ ; 31-40 % Ba ²⁺ ; 1-3. 9% Cu ²⁺ ; 6. 5-10% Zn ²⁺ ; 0 ² — and the total amount of F- is more than 99%; CI—, Br— and I—the total amount is 0. 009-0. 1%.

9. A near-infrared light absorbing glass characterized by comprising 15-40% of P ⁵⁺ ; 5-20% of Al ³⁺ ;

The content of R+ is 1-35%; the content of T ²⁺ is 30-55%; 0. 1-4% Cu ²⁺ ; 1-15% Zn ²⁺ ; 0 ² — and F- 96% or more, the R ⁺ represents a total amount of Li ⁺ , Na ⁺ and K ⁺ , and the Τ ²⁺ represents a total amount of Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ .

The near-infrared light absorbing glass according to claim 9, which comprises 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; R + is 3-30%; T ²⁺ The content of 40-50%; 0. 5-3. 9% Cu ²⁺ ; more than 6% but less than 12% of Zn ²⁺ ; 0 ² - and F - the total amount is 97% or more.

The near-infrared light absorbing glass according to claim 9, which comprises 25-30% of P ⁵⁺ ; 10-15% of Al ³⁺ ; R + is 5-15%; T ²⁺ The content is 42-48%; 1-3. 9% Cu ²⁺ ; 6. 5-10% Zn ²⁺ ; 0 ² - and F-- total amount is 99% or more.

The near-infrared light absorbing glass according to claim 9, which contains 15-40% of P ⁵⁺ ; 5-20% of Al ³⁺ ; 1-15% of Li + ; 0 -15 % Na+; 0-5% K+; 0. 1-10% Mg ²⁺ _; 1-20% Ca ²⁺ ; 0-15% Sr ²⁺ ; more than 30% but less than 45% Ba ²⁺ ; 0. 1-4% Cu ²⁺ ;

1-15% of Zn ^_2+; 0 ² - and the total amount of F- is less than 96%; CI, Br- and I is the total amount of 0. 001-1%.

The near-infrared light absorbing glass according to claim 9, which contains 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-10% of Li + ; 1-12% Na+; 0-5% K+; 2-8% Mg ²⁺ ; 3-15% Ca ²⁺ ; 0-10% Sr ²⁺ ; 31-42% 8&²⁺; 0. 5-3 9% of the Cu ^2+; greater than 6% but less than 12% of Zn ^2+; 0 ² - and the total amount of F- is less than 97%; total amount of Cl, Br- and I is 0. 005-0. 5

The near-infrared light absorbing glass according to claim 9, which comprises 25-30% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-6% of Li + ; 2-10% Na ⁺ ; 0-5% K ⁺ ; 3-7% Mg ²⁺ ; 5- 11% Ca ²⁺ ; 0-5% Sr ²⁺ ; 31- 40% Ba ²⁺ ; 1-3 9% Cu ²⁺ ; 6. 5- 10% Zn ²⁺ ;

009-0. 1%。 The total amount of 0 ² - and F - is more than 99%; the total amount of Cl -, Br - and I - is 0. 009-0. 1%.

The near-infrared light absorbing glass according to claim 9, which comprises 15 to 40% of P ⁵⁺ ; 5 to 20% of Al ³⁺ ; 1-15% of Li + ; 0 to 15% Na+; 0-5% K+; 0. 1-10%

Mg ²⁺ _; 1-20% Ca ²⁺ ; 0-15% Sr ²⁺ ; greater than 30% but less than 45% Ba ²⁺ ; 0. 1-4% Cu ²⁺ ;

1-15% of Zn ²⁺ ; the total amount of Ba ²⁺ and Na ⁺ is more than 30% but less than 60%; 50-70% of 0 ² -; 30-50% of F-; CI-, Br- and 001-1%。 The total amount of I - 0. 001-1%.

The near-infrared light absorbing glass according to claim 9, which comprises 20-35% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-10% of Li + ; 1-12% Na+; 0-5% K+; 2-8% Mg ²⁺ ;

3-15% Ca ²⁺ ; 0-10% Sr ²⁺ ; 31-42% 8&²⁺; 0. 5-3. 9% Cu ²⁺ ; more than 6% but less than 12% Zn ^{2 +} ; the total amount of Ba ²⁺ and Na ⁺ is 32-50%; 55-65% of 0 ² -; 35-45% of F-;

005-0. 5%。 The total amount of CI-, Br- and I is 0. 005-0. 5%.

The near-infrared light absorbing glass according to claim 9, which contains 25-30% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-6% of Li + ; 2-10% Na ⁺ ; 0-5% K ⁺ ; 3-7% Mg ²⁺ ;

5- 11% Ca ²⁺ ; 0-5% Sr ²⁺ ; 31- 40% Ba ²⁺ ; 1-3. 9% Cu ²⁺ ; 6. 5- 10% Zn ²⁺ ;

009-0. 1 The total amount of Ba ²⁺ and Na ⁺ is 33-46%; 57-63% of 0 ² -; 37-43% of F-; CI-, Br- and I are 0. 009-0. %.

The near-infrared light absorbing glass according to claim 9, which comprises 25-30% of P ⁵⁺ ; 10-15% of Al ³⁺ ; 2-6% of Li + ; 2-10% Na ⁺ ; 0-5% K ⁺ ; 3-7% Mg ²⁺ ;

57-63% of 0 ² —; 37-43% of F—; 0. 01-0. 07% of C1—.

The near-infrared light absorbing glass according to claim 9, wherein in the spectral transmittance of the wavelength of 400 to 700 nm, the transmittance of the glass shows that the wavelength of 50% is 615 nm.

0. 2-0. 5mm between.

A near-infrared light absorbing member comprising the near-infrared light absorbing glass according to any one of claims 1 to 19.

A near-infrared light absorbing filter comprising the near-infrared light absorbing glass according to any one of claims 1 to 19.