CN107176788A

CN107176788A - Near-infrared absorption glass, element and filter

Info

Publication number: CN107176788A
Application number: CN201710368576.7A
Authority: CN
Inventors: 孙伟; 匡波; 赖德光
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: CDGM Glass Co Ltd; Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2012-04-11
Filing date: 2012-04-11
Publication date: 2017-09-19
Also published as: JP6047227B2; KR101677825B1; CN102923949A; KR20150005963A; JP2015522500A; WO2013152629A1

Abstract

The present invention provide a kind of environmentally friendly, thickness of glass it is relatively thin, with superior chemical stability, in the near-infrared absorption glass of the excellent transmission characteristic of visible range, and the near-infrared absorption element and filter being made up of the glass.Near-infrared absorption glass, when the near-infrared absorption thickness of glass is 0.4mm, shows more than 80% in wavelength 400nm transmitances, shows that, more than 83%, the near-infrared absorption glass contains the P that useful cation form shows in wavelength 500nm transmitances⁵⁺、Al³⁺、R⁺、T²⁺、Zn²⁺And Cu²⁺, the R⁺Represent Li⁺、Na⁺And K⁺Total amount, the T²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount, Cu²⁺Content is more than 4% but less than or equal to 12%, Zn²⁺Content be 1 15%, while the O represented containing useful anion^2‑And F^‑。

Description

Near-infrared absorption glass, element and filter

The application is to be directed to Application No. 201210104359.4, and the applying date is on April 11st, 2012, entitled " near red The divisional application of the application for a patent for invention of outer light absorbs glass, element and filter ".

Technical field

The present invention relates to the optical filtering of a kind of near-infrared absorption glass, near-infrared absorption element and near-infrared absorption Device.In particular it relates to which a kind of near-infrared absorption filter of suitable chromatic sensitivity amendment is used, chemical stability is excellent Near-infrared absorption glass, and the near-infrared absorption element and filter being made up of the glass.

Background technology

In recent years, the spectrum sensitivity for semiconductor camera elements such as CCD, CMOS of digital camera and VTR cameras Degree, spreads to since the near-infrared field visual field near 1100nm, can using the filter for absorbing near-infrared field light To obtain being similar to the visual sense degree of people.Therefore, the demand of chromatic sensitivity amendment filter is increasing, and this is just to for manufacturing The near-infrared absorption functional glass of such filter proposes higher requirement, that is, is required to a large amount of, qurer and supplies this Class glass, and glass has preferable stability.

In the prior art, near-infrared ray absorption glass is by adding Cu in phosphate glass or fluorphosphate glass²⁺ To manufacture near-infrared absorption glass.But for relative fluorphosphate glass, phosphate glass chemical stability is poor, glass If be exposed to for a long time under hot and humid environment, glass surface can produce the defect of cracking and gonorrhoea.Prior art is also led to Cross introducing Sb³⁺To eliminate Cu in glass solution²⁺It is reduced to Cu⁺, to solve the skill of the transmitance reduction near glass wavelength 400nm Art problem, but Sb₂O₃Introducing environment is affected.

In addition, the miniaturization of photoelectricity end product, lightweight promote the thin plate of near-infrared absorption filter glass.But It is if that, directly that glass is thinning, near-infrared absorption also diminishes, it is impossible to required dichroism is obtained, so often leading to Cross increase coloring components Cu²⁺Content reduced with making up to absorb caused by thin plate, and near-infrared absorption filter glass Cu²⁺ The high then Cu of concentration²⁺Valence mumber change, transmitance reduction near 400nm and be changed into blue-green.In addition, if increase Cu²⁺'s Crystal is easily separated out in amount, then glass devitrification resistance deterioration, glass.

The content of the invention

The technical problems to be solved by the invention be to provide a kind of environmentally friendly, thickness of glass it is relatively thin, with superior chemistry Stability, the near-infrared absorption glass in the excellent transmission characteristic of visible range, and the near-infrared absorption being made up of the glass Element and filter.

The present invention solves the technical scheme that is used of above-mentioned technical problem：Near-infrared absorption glass, the near-infrared When light absorbs thickness of glass is 0.4mm, shows more than 80%, shown greatly in wavelength 500nm transmitances in wavelength 400nm transmitances In 83%, the near-infrared absorption glass contains the P that useful cation form shows⁵⁺、Al³⁺、R⁺、T²⁺、Zn²⁺And Cu²⁺, the R⁺Generation Table Li⁺、Na⁺And K⁺Total amount, the T²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount, Cu²⁺Content be more than 4% but Less than or equal to 12%, Zn²⁺Content be 1-15%, while the O represented containing useful anion^2-And F^-。

Further, when the near-infrared absorption thickness of glass is 0.4mm, shows and be more than in wavelength 400nm transmitances 88%, shown in wavelength 500nm transmitances more than 90%.

Further, the P containing 15-40%⁵⁺；5-20% Al³⁺；R⁺Content be 1-35%；T²⁺Content be 30- 55%；Cu more than 4% but less than or equal to 12%²⁺；1-15% Zn²⁺；O^2-And F^-Total amount be more than 96%.

Further, the P containing 20-35%⁵⁺；10-15% Al³⁺；R⁺Content be 3-30%；T²⁺Content be 40- 50%；4.1-10% Cu²⁺；Zn more than 6% but less than 12%²⁺；O^2-And F^-Total amount be more than 97%.

Further, the P containing 25-30%⁵⁺；10-15% Al³⁺；R⁺Content be 5-15%；T²⁺Content be 42- 48%；4.1-9% Cu²⁺；6.5-10% Zn²⁺；O^2-And F^-Total amount be more than 99%.

Further, the P containing 15-40%⁵⁺；5-20% Al³⁺；1-15% Li⁺；0-15% Na⁺；0-5% K⁺；0.1-10% Mg²⁺；1-20% Ca²⁺；0-15% Sr²⁺；Ba more than 30% but less than 45%²⁺；It is more than 4% but small In or equal to 12% Cu²⁺；1-15% Zn²⁺；O^2-And F^-Total amount be more than 96%；Cl^-、Br^-And I^-Total amount be 0.001-1%.

Further, the P containing 20-35%⁵⁺；10-15% Al³⁺；2-10% Li⁺；1-12% Na⁺；0-5%'s K⁺；2-8% Mg²⁺；3-15% Ca²⁺；0-10% Sr²⁺；31-42% Ba²⁺；4.1-10% Cu²⁺；It is more than 6% but small In 12% Zn²⁺；O^2-And F^-Total amount be more than 97%；Cl^-、Br^-And I^-Total amount be 0.005-0.5%.

Further, the P containing 25-30%⁵⁺；10-15% Al³⁺；2-6% Li⁺；2-10% Na⁺；0-5% K⁺；3-7% Mg²⁺；5-11% Ca²⁺；0-5% Sr²⁺；31-40% Ba²⁺；4.1-9% Cu²⁺；6.5-10% Zn² ⁺；O^2-And F^-Total amount be more than 99%；Cl^-、Br^-And I^-Total amount be 0.009-0.1%.

Near-infrared absorption glass, the P containing 15-40%⁵⁺；5-20% Al³⁺；R⁺Content be 1-35%；T²⁺Contain Measure as 30-55%；Cu more than 4% but less than or equal to 12%²⁺；1-15% Zn²⁺；O^2-And F^-Total amount for 96% with On, the R⁺Represent Li⁺、Na⁺And K⁺Total amount, the T²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount.

Further, the P containing 15-40%⁵⁺；5-20% Al³⁺；1-15% Li⁺；0-15% Na⁺；0-5% K⁺；0.1-10% Mg²⁺；1-20% Ca²⁺；0-15% Sr²⁺；Ba more than 30% but less than 45%²⁺；It is more than 4% but small In or equal to 12% Cu²⁺；1-15% Zn²⁺；0-2% Si⁴⁺；Ba²⁺With Na⁺Total amount be more than 30% but to be less than 60%；50-70% O^2-；30-50% F^-；Cl^-、Br^-And I^-Total amount be 0.001-1%.

Further, the P containing 20-35%⁵⁺；10-15% Al³⁺；2-10% Li⁺；1-12% Na⁺；0-5%'s K⁺；2-8% Mg²⁺；3-15% Ca²⁺；0-10% Sr²⁺；31-42% Ba²⁺；4.1-10% Cu²⁺；It is more than 6% but small In 12% Zn²⁺；0-1% Si⁴⁺；Ba²⁺With Na⁺Total amount be 32-50%；55-65% O^2-；35-45% F^-； Cl^-、Br^-And I^-Total amount be 0.005-0.5%.

Further, the P containing 25-30%⁵⁺；10-15% Al³⁺；2-6% Li⁺；2-10% Na⁺；0-5% K⁺；3-7% Mg²⁺；5-11% Ca²⁺；0-5% Sr²⁺；31-40% Ba²⁺；4.1-9% Cu²⁺；6.5-10% Zn² ⁺；0.1-1% Si⁴⁺；Ba²⁺With Na⁺Total amount be 33-46%；57-63% O^2-；37-43% F^-；Cl^-、Br^-And I^- Total amount be 0.009-0.1%.

Further, the P containing 25-30%⁵⁺；10-15% Al³⁺；2-6% Li⁺；2-10% Na⁺；0-5% K⁺；3-7% Mg²⁺；5-11% Ca²⁺；0-5% Sr²⁺；31-40% Ba²⁺；4.1-9% Cu²⁺；6.5-10% Zn² ⁺；0.1-1% Si⁴⁺；57-63% O^2-；37-43% F^-；0.01-0.07% Cl^-。

Further, in wavelength 400-700nm spectral transmittances, the transmitance of glass shows that 50% wavelength is 615nm thickness is between 0.3-0.6mm.

Near-infrared absorption element, is made up of above-mentioned near-infrared absorption glass.

Near-infrared absorption filter, is made up of above-mentioned near-infrared absorption glass.

The beneficial effects of the invention are as follows：The present invention is made up of specific glass and designed, and matrix is used as using fluophosphate glass Glass, introduces appropriate Zn²⁺So that chemical durability of glass is excellent, glass is water-fast to act on stability D_W(powder method) reaches 1 grade, Acidproof effect stability D_A(powder method) reaches or better than 4 grades；Simultaneously Sr is not preferably introduced in glass composition²⁺, increase Ba²⁺Content To improve glass alkalescence, be conducive to Cu²⁺Presence, make glass Near-infrared Spectral Absorption excellent performance of the present invention, glass of the invention When glass thickness is 0.4mm, wavelength 400nm transmitances are shown more than 80%, are shown in wavelength 500nm transmitances more than 83%, In spectral transmittance in 500 to 700nm wave-length coverage, corresponding wavelength (λ when transmitance is 50%₅₀Corresponding wavelength Value) scope be 605-630nm scope.

Brief description of the drawings

Fig. 1 is the spectral transmittance curve map of the near-infrared absorption glass of embodiments of the invention 1.

Embodiment

The near-infrared absorption glass of the present invention is based on fluophosphate glass, added with near-infrared absorption effect Cu²⁺Obtained from.

Hereinafter, cationic componentses content accounts for the degree table of whole cation gross weights with the cation weight Show, the degree that anionic group content accounts for whole anion gross weights with the anion weight is represented.

P⁵⁺It is in Cu for the basis of fluorphosphate glass²⁺Region of ultra-red in produce a kind of important set of absorption Point.When its content is less than 15%, colour correction function deteriorates and with green；More than 40% weather resisteant, devitrification resistance deteriorate, because This P⁵⁺Content be defined to 15-40%, more preferably preferably 20-35%, 25-30%.

Al³⁺It is devitrification repellence, weatherability, resistance to sudden heating, mechanical strength and resistance toization for improving fluorphosphate glass A kind of component for the property learned.Work as Al³⁺When content is less than 5%, the effect above is not reached；Work as Al³⁺When content is more than 20%, near-infrared Line absorption characteristic is reduced.Therefore, Al³⁺Content is 5-20%, more preferably 10-15%.

R⁺It is meltability, the component into glassy and visible region transmitance for improving glass.Here R⁺Represent Li⁺、 Na⁺And K⁺Total amount, if R⁺Content more than 35%, the chemical durability of glass can be reduced substantially.Therefore, R⁺It is total to contain Amount scope is 1-35%, and preferred content is 3-30%, and more preferably content is 5-15%.

Relative to Na⁺、K⁺For, Li⁺Introducing it is more preferable to the chemical stability effect of glass.But work as Li⁺Content exceedes When 20%, the durability and processing characteristics of glass deteriorate.Therefore, Li⁺Content is 1-15%, preferably 2-10%, more preferably 2-6%.

The present invention can also be preferably added to a small amount of Na⁺With Li⁺Consolute, can effectively improve the weather resisteant of glass, while can be bright The aobvious alkalescence for improving glass metal, makes the near-infrared absorption excellent performance of glass.Na⁺Content is 0-15%, preferably 1-12%, More preferably 2-10%.K⁺Content is 0-5%, if its content is more than 5%, durability of glass is reduced on the contrary.

T²⁺Be effectively improve glass into glassy, devitrification resistance and the component of machinability, T here²⁺Represent Mg²⁺、 Ca²⁺、Sr²⁺And Ba²⁺.As near-infrared absorption filter, the light transmission rate for being contemplated to be visible range is higher.It is visual in order to improve The transmitance in domain, the copper ion of introducing is not Cu⁺, it is necessary to it is Cu²⁺.If glass solution is in reducing condition, Cu²⁺Reform into Cu⁺, the result is that the transmitance near wavelength 400nm will be reduced.T of the present invention²⁺If total amount less than 30%, devitrification Property just have the tendency of deterioration, if it exceeds 55%, also have the tendency of to deteriorate devitrification resistance.Therefore, T²⁺Total content is 30- 55%, it is 40-50% preferably to add up to content, and it is 42-48% more preferably to add up to content.

Wherein, Mg²⁺And Ca²⁺It is improved the effect of glass devitrification resistance, chemical stability, processability.Mg²⁺Content is 0.1-10% is more satisfactory, more preferably 2-8%, further preferred 3-7%.Ca²⁺Content is preferably 1-20%, more preferably 3- 15%, it is still more preferably 5-11%.

Ba²⁺And Sr²⁺With the effect for improving into glassy, glass devitrification resistance, meltbility.Wherein Ba²⁺Content is preferably More than 30% but less than 45%, more preferably 31-42%, most preferably 31-40%.Sr²⁺Content is preferably 0-15%, more preferably For 0-10%, most preferably 0-5%.

In addition, the present invention introduces the Ba of high content in being mainly made up of glass²⁺, preferably do not introduce Sr²⁺, reaching has Effect improves the goal of the invention of the chemical stability of glass, and by adjusting Ba²⁺With Na⁺Total amount, glass can be effectively increased Alkalescence is to improve its near-infrared absorption performance.Ba²⁺With Na⁺Total amount be preferably greater than 30% but less than 60%, further Preferably 32-50%, more preferably 33-46%.

The present invention is by introducing Zn²⁺, the alkalescence of glass metal can be effectively improved, and the alkaline environment of glass metal is conducive to copper Ion is with Cu²⁺Form exist so that more Cu can be introduced in host glass²⁺, to improve glass near-infrared absorption Energy；In other inventive formulation composition, Zn²⁺With P⁵⁺Effect can make chemical durability of glass excellent, particularly the water resistance of glass Can be excellent；Therefore, Zn²⁺Content be 1-15%, preferred scope is that, more than 6% but less than 12%, more preferably scope is 6.5- 10%.

In addition, Si⁴⁺The stability of glass melting can be effectively improved.But, if Si⁴⁺Too high levels, can reduce glass Fusible property, so that necessary elevated melting temperature, can reduce Cu ions so that bringing the wind of reduction colour sensitivity calibration function Danger.Therefore, Si⁴⁺Content range 0-2%, preferably 0-1%, more preferably 0.1-1%.

Copper in glass is the leading indicator of near-infrared absorbing characteristic, and with Cu²⁺In the presence of.Work as Cu²⁺Content is 4% When following, near-infrared absorbing is few, does not reach the required spectrum property of the present invention；But when its content is more than 12%, the present invention The devitrification resistance property reduction of glass.Therefore, Cu²⁺Content is more than 4 but is less than or equal to 12%, preferably 4.1-10%, more excellent Elect 4.1-9% as.

Contain the O as anion component in glass of the present invention^2-And F^-。O^2-It is a kind of important the moon in glass of the present invention Ion component, works as O^2-Content very little when because Cu²⁺It is reduced to Cu⁺, so in short wavelength region, it is particularly attached in 400nm Near absorption is become much larger until shown in green；But work as O^2-Content it is excessive when because the viscosity of glass become it is higher so as to Cause higher melting temperature, so transmitance is reduced.Therefore, O in the present invention^2-Content be 50-70%, preferably 55- 65%, more preferably 57-63%.

In near-infrared ray absorption glass, when improving melting temperature, Cu²⁺Easily it is reduced to Cu⁺, the color of glass is from indigo plant Discoloration is green, so as to compromise necessary characteristic in colour sensitivity correct application to semiconductor image-forming component.This hair Bright preferred appropriate F^-Content, makes the chemical stability of glass excellent.Therefore, F^-Preferred scope be 30-50%, further it is excellent Elect 35-45% as, most preferred range is 37-43%.

In addition, in order to remove the bubble produced in glass melting process, except the O as anion component^2-And F^-, Cl^-、 Br^-And I^-It is comparatively ideal that the one or more kinds of fining agent of middle selection, which is introduced,.If Cl^-、Br^-And I^-Total amount not If 0.001%, it is difficult to fully obtain removing the bubble produced in glass melting process, if total amount is more than 1%, Cu²⁺Cu can be reduced into⁺, the transmitance near wavelength 400nm deteriorates.Therefore, Cl of the invention^-、Br^-And I^-Total contain Measure as 0.001-1%, preferred content is 0.005-0.5%, more preferably content is 0.009-0.1%, and most preferred content is 0.01- 0.07%.

In Cl^-、Br^-And I^-In, that best embody superior effect is Cl^-, therefore, in Cl^-、Br^-And I^-In, preferably Only add Cl^-。Cl^-Amount is 0.001-1%, and preferred content is 0.005-0.5%, and more preferably content is 0.009-0.1%, Most preferred content is 0.01-0.07%.

It in fluophosphate glass, anion component is largely O that the near-infrared absorption glass of the present invention, which is,^2-And F^-.That is, make For O^2-And F^-Total amount, more than 95% can be assign as target.Make the present invention glass reach superior weatherability, Maintain the high transmittance near wavelength 400nm, realize superior devitrification resistance, O^2-And F^-Total amount for 96% with On, it is more than 97% more preferably to add up to amount, further preferably more than 99%.

The characteristic to glass of the present invention is explained below.

The transmitance of glass is with thickness change, if it is known that light passes through the thickness of glass and transmitance in direction, then The transmitance of specific thickness can be obtained by calculating.

When thickness of glass of the present invention is 0.4mm, under the spectral transmittance in 400nm to 1200nm wave-length coverage has The characteristic that face is shown.

400nm wavelength spectral transmittance be more than or equal to 80%, preferably greater than or equal to 85%, more preferably greater than Or equal to 88%.

500nm wavelength spectral transmittance be more than or equal to 83%, preferably greater than or equal to 88%, more preferably greater than Or equal to 90%.

600nm wavelength spectral transmittance be more than or equal to 50%, preferably greater than or equal to 55%, more preferably greater than Or equal to 60%.

700nm wavelength spectral transmittance be less than or equal to 15%, preferably lower than or equal to 10%, more preferably less than Or equal to 8%.

800nm wavelength spectral transmittance be less than or equal to 8%, preferably lower than or equal to 5%, more preferably less than or Equal to 3%, even more preferably less than or equal to 2%.

900nm wavelength spectral transmittance be less than or equal to 10%, preferably lower than or equal to 5%, more preferably less than Or equal to 2.8%.

1000nm wavelength spectral transmittance be less than or equal to 10%, preferably lower than or equal to 7%, more preferably less than Or equal to 5.8%.

1100nm wavelength spectral transmittance be less than or equal to 15%, preferably lower than or equal to 13%, it is more preferably small In or equal to 12.5%.

1200nm wavelength spectral transmittance be less than or equal to 28%, preferably lower than or equal to 26%, it is more preferably small In or equal to 23.5%.

When thickness of glass i.e. of the present invention is 0.4mm, the absorption in 700nm to 1200nm near infrared region wave-length coverage Greatly, the absorption in 400nm to 600nm visible region wave-length coverage is small.Light in 500 to 700nm wave-length coverage Compose in transmitance, corresponding wavelength (λ when transmitance is 50%₅₀Corresponding wavelength value) scope be 605-630nm, preferred scope For 610-625nm, more preferably 612-620nm.

Moreover, in wavelength 400-700nm spectral transmittances, glass transmitance of the present invention shows that 50% wavelength is 615nm thickness is between 0.1-0.8mm, preferably between 0.2-0.6mm, more preferably between 0.3-0.6mm.It is preferred that institute The transmitance of wavelength 400nm under thickness is stated more than 80%.

Thickness of the present invention is that the transmitance of 0.4mm glass refers to that its wavelength of the glass determined with spectrophotometer is 400- 1200nm transmitance.Transmitance determines obtained value in this way：It is assumed that there is glass sample parallel to each other and optics to throw Two planes of light, light is from vertical incidence on a parallel plane, from another parallel plane outgoing, the intensity of the emergent light Divided by the intensity of incident light is exactly transmitance, the transmitance is also referred to as outer transmitance.

According to the above-mentioned characteristic of the glass of the present invention, it can admirably realize semiconductor image-forming component such as CCD or CMOS Color correction.

Characteristic in terms of the chemical stability of glass is as follows：Water-fast effect stability D_W1 grade can be reached；Acidproof effect is steady Qualitative D_A4 grades are reached, 3 grades, more preferably up to 2 grades are preferably reached.

Above-mentioned water-fast effect stability D_W(powder method) presses GB/T17129 method of testing, is calculated according to following formula：

D_W=(B-C)/(B-A) * 100

In formula：D_W- glass leaches percentage (%)

The quality (g) of B-filter and sample

The quality (g) of sample after C-filter and erosion

A-filter quality (g)

By the leaching percentage calculated, by the stable D of the water-fast effect of optical glass_WIt is divided into 6 classes see the table below.

Above-mentioned acidproof effect stability D_A(powder method) presses GB/T17129 method of testing, is calculated according to following formula：

D_A=(B-C)/(B-A) * 100

In formula：D_A- glass leaches percentage (%)

The quality (g) of B-filter and sample

The quality (g) of sample after C-filter and erosion

A-filter quality (g)

By the leaching percentage calculated, by the stable D of the acidproof effect of optical glass_AIt is divided into 6 classes see the table below.

The near-infrared absorption element that the present invention relates to is made up of the near-infrared absorption glass, can be included For laminal glass elements or lens in near-infrared absorption filter etc., it is adaptable to the colour correction of solid-state imager Purposes, possesses good through performance and chemical stability.Moreover, the thickness of near-infrared absorption element is (through the incidence of light Face and the interval of outgoing plane) determined by the light transmission rate of the element, preferably between about 0.1-0.8mm, more preferably exist Determined between 0.3-0.6mm, and preferably λ₅₀Between 605-630nm, particularly preferred 615nm.It is such near red in order to obtain Outer light absorbing elements, adjust the composition of near-infrared absorption glass, are processed into the element with above-mentioned spectral characteristic thickness.

The near infrared filter device that the present invention relates to is the near-infrared absorption member being made up of near-infrared absorption glass Part is constituted, and is possessed two sides by optical grinding, the near-infrared absorption element that near-infrared absorption glass is constituted, is passed through this member Part assigns the colour correction function of filter, while also possessing good chemical stability.

Embodiment

Hereinafter, the present invention will be described in further detail in reference implementation example.However, the invention is not restricted to the embodiment.

First, using fluoride, metaphosphate, oxide, nitrate and carbonate as frit, raw material, which is weighed, to be made It is the glass with the composition being displayed in Table 1, and after being thoroughly mixed, mixed material is put into the sealed platinum earthenware of lid In crucible, melting is heated at a temperature of 700-900 DEG C, clarification is homogenized using oxygen protection simultaneously after, makes melten glass from temperature control Flowed continually out in pipeline with constant flow rate, the optical glass of the present invention is obtained after shaping.

Table 1

By above-mentioned glass processing into tabular, and two sides relative to each other is carried out optical polish to prepare for measuring The sample of rate is crossed, the spectral transmittance of each sample is measured using spectral transmission instrument, the allusion quotation of each sample of 0.4mm thickness is obtained The transmitance of type wavelength.

The glass is shown in table 2 in 0.4mm thickness, the transmitance value of glass of the present invention, it can be verified that the glass Glass all has the excellent properties that glass is corrected as the colour sensitivity for semiconductor image-forming component.

Table 2

Table 3 illustrates embodiment 1-10 glass, is 50% corresponding thickness of glass in wavelength 615nm transmitance, with And wavelength is respectively the spectral transmittance under 400nm, 600nm, 800nm, 1000nm, 1200nm under the thickness.

Table 3

Fig. 1 is the spectral transmittance curve map of above-described embodiment 1.It can be seen that being 0.4mm's in thickness of glass In the case of, optimal wavelength 400nm transmitance is more than 85%.Spectral transmittance in 500 to 700nm wave-length coverage In, corresponding wavelength (λ when transmitance is 50%₅₀Corresponding wavelength value) scope be 610-630nm.In wavelength 400-1200nm Spectral transmittance in, the transmitance of wavelength 800-1000nm wavelength zone is minimum.Because this region is near-infrared region, partly lead Susceptibility of the body photographing element in the region is not very low, it is therefore necessary to suppresses the transmitance of colour correction filter, reaches it To substantially low degree.And when region of the wavelength in 1000-1200nm, the susceptibility relative reduction of semiconductor image-forming component, Therefore the transmitance of the glass of the present invention increased.

Claims

1. near-infrared absorption glass, it is characterised in that when the near-infrared absorption thickness of glass is 0.4mm, in wavelength 400nm transmitances are shown more than 80%, show that the near-infrared absorption glass contains more than 83% in wavelength 500nm transmitances The P that useful cation is represented⁵⁺、Al³⁺、R⁺、T²⁺、Zn²⁺And Cu²⁺, the R⁺Represent Li⁺、Na⁺And K⁺Total amount, the T²⁺Generation Table Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount, Cu²⁺Content is more than 4% but less than or equal to 12%, Zn²⁺Content be 1- 15%, while the O represented containing useful anion^2-And F^-。

2. near-infrared absorption glass as claimed in claim 1, it is characterised in that the near-infrared absorption thickness of glass is During 0.4mm, show more than 88%, shown in wavelength 500nm transmitances more than 90% in wavelength 400nm transmitances.

3. near-infrared absorption glass as claimed in claim 1 or 2, it is characterised in that the P containing 15-40%⁵⁺；5-20% Al³⁺；R⁺Content be 1-35%；T²⁺Content be 30-55%；Cu more than 4% but less than or equal to 12%²⁺；1-15% Zn²⁺；O^2-And F^-Total amount be more than 96%.

4. near-infrared absorption glass as claimed in claim 1 or 2, it is characterised in that the P containing 20-35%⁵⁺；10-15% Al³⁺；R⁺Content be 3-30%；T²⁺Content be 40-50%；4.1-10% Cu²⁺；Zn more than 6% but less than 12%² ⁺；O^2-And F^-Total amount be more than 97%.

5. near-infrared absorption glass as claimed in claim 1 or 2, it is characterised in that the P containing 25-30%⁵⁺；10-15% Al³⁺；R⁺Content be 5-15%；T²⁺Content be 42-48%；4.1-9% Cu²⁺；6.5-10% Zn²⁺；O^2-And F^-'s Total amount is more than 99%.

6. near-infrared absorption glass as claimed in claim 1 or 2, it is characterised in that the P containing 15-40%⁵⁺；5-20% Al³⁺；1-15% Li⁺；0-15% Na⁺；0-5% K⁺；0.1-10% Mg²⁺；1-20% Ca²⁺；0-15% Sr² ⁺；Ba more than 30% but less than 45%²⁺；Cu more than 4% but less than or equal to 12%²⁺；1-15% Zn²⁺；O^2-And F^-'s Total amount is more than 96%；Cl^-、Br^-And I^-Total amount be 0.001-1%.

7. near-infrared absorption glass as claimed in claim 1 or 2, it is characterised in that the P containing 20-35%⁵⁺；10-15% Al³⁺；2-10% Li⁺；1-12% Na⁺；0-5% K⁺；2-8% Mg²⁺；3-15% Ca²⁺；0-10% Sr²⁺； 31-42% Ba²⁺；4.1-10% Cu²⁺；Zn more than 6% but less than 12%²⁺；O^2-And F^-Total amount be more than 97%； Cl^-、Br^-And I^-Total amount be 0.005-0.5%.

8. near-infrared absorption glass as claimed in claim 1 or 2, it is characterised in that the P containing 25-30%⁵⁺；10-15% Al³⁺；2-6% Li⁺；2-10% Na⁺；0-5% K⁺；3-7% Mg²⁺；5-11% Ca²⁺；0-5% Sr²⁺；31- 40% Ba²⁺；4.1-9% Cu²⁺；6.5-10% Zn²⁺；O^2-And F^-Total amount be more than 99%；Cl^-、Br^-And I^-'s Total amount is 0.009-0.1%.

9. near-infrared absorption glass, it is characterised in that the P containing 15-40%⁵⁺；5-20% Al³⁺；R⁺Content be 1- 35%；T²⁺Content be 30-55%；Cu more than 4% but less than or equal to 12%²⁺；1-15% Zn²⁺；O^2-And F^-It is total Measure as more than 96%, the R⁺Represent Li⁺、Na⁺And K⁺Total amount, the T²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺It is total Amount.

10. near-infrared absorption glass, it is characterised in that the P containing 15-40%⁵⁺；5-20% Al³⁺；T²⁺Content be 30- 55%；Cu more than 4% but less than or equal to 12%²⁺；1-15% Zn²⁺；1-15% Li⁺；0-15% Na⁺；0-5%'s K⁺, O^2-And F^-Total amount be more than 96%, the T²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount.

11. near-infrared absorption glass, it is characterised in that the P containing 15-40%⁵⁺；5-20% Al³⁺；1-35% R⁺； 0.1-10% Mg²⁺；1-20% Ca²⁺；0-15% Sr²⁺；Ba more than 30% but less than 45%²⁺；More than 4% but it is less than Or the Cu equal to 12%²⁺；1-15% Zn²⁺；O^2-And F^-Total amount be more than 96%, the R⁺Represent Li⁺、Na⁺And K⁺Conjunction Metering.

12. the near-infrared absorption glass as described in claim 9-11 any claims, it is characterised in that wherein：P⁵⁺： 20-35%；And/or Al³⁺：10-15%；And/or T²⁺：40-50%；And/or R⁺：3-30%；And/or Zn²⁺：It is more than 6% but small In 12%；And/or Cu²⁺：4.1-10%；And/or Li⁺：2-10%；And/or Na⁺：1-12%；And/or Mg²⁺：2-8%；And/or Ca²⁺：3-15%；And/or Sr²⁺：0-10%；And/or Ba²⁺：31-42%, the R⁺Represent Li⁺、Na⁺And K⁺Total amount, institute State T²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount.

13. the near-infrared absorption glass as described in claim 9-11 any claims, it is characterised in that wherein：P⁵⁺： 25-30%；And/or T²⁺：42-48%；And/or R⁺：5-15%；And/or Zn²⁺：6.5-10%；And/or Cu²⁺：4.1-9%； And/or Li⁺：2-6%；And/or Na⁺：2-10%；And/or Mg²⁺：3-7%；And/or Ca²⁺：5-11%；And/or Sr²⁺：0-5%； And/or Ba²⁺：31-40%, the R⁺Represent Li⁺、Na⁺And K⁺Total amount, the T²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺'s Total amount.

14. the near-infrared absorption glass as described in claim 9-11 any claims, it is characterised in that contain 50- 70% O^2-；30-50% F^-；Preferably comprise 55-65% O^2-；35-45% F^-；Further preferably 57-63% O^2-； 37-43% F^-。

15. the near-infrared absorption glass as described in claim 9-11 any claims, it is characterised in that Ba²⁺With Na⁺'s Total amount is more than 30% but less than 60%；Preferably 32-50%；More preferably 33-46%.

16. the near-infrared absorption glass as described in claim 9-11 any claims, it is characterised in that Cl^-、Br^-With I^-Total amount be 0.001-1%；Preferably 0.005-0.5%；More preferably 0.009-0.1%；More preferably contain 0.01-0.07% Cl^-。

17. the near-infrared absorption glass as described in claim 9-11 any claims, it is characterised in that O^2-And F^-Conjunction Measure as more than 97%；Preferably O^2-And F^-Total amount be more than 99%.

18. the near-infrared absorption glass as described in claim 1,9-11 any claims, it is characterised in that also contain 0- 2% Si⁴⁺；It is preferred that 0-1% Si⁴⁺；More preferably 0.1-1% Si⁴⁺。

19. the near-infrared absorption glass as described in claim 1, any rights of 9-11, it is characterised in that in wavelength 400- In 700nm spectral transmittances, the transmitance of glass shows thickness of 50% wavelength for 615nm between 0.3-0.6mm.

20. near-infrared absorption element, it is characterised in that as the near infrared light described in any claim in claim 1-19 Heat absorbing glass is constituted.

21. near-infrared absorption filter, it is characterised in that as the near-infrared described in any claim in claim 1-19 Light absorbs glass is constituted.